TWI663608B - Conductive resin composition and semiconductor device - Google Patents
Conductive resin composition and semiconductor device Download PDFInfo
- Publication number
- TWI663608B TWI663608B TW104102152A TW104102152A TWI663608B TW I663608 B TWI663608 B TW I663608B TW 104102152 A TW104102152 A TW 104102152A TW 104102152 A TW104102152 A TW 104102152A TW I663608 B TWI663608 B TW I663608B
- Authority
- TW
- Taiwan
- Prior art keywords
- resin composition
- silver
- conductive resin
- particles
- meth
- Prior art date
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/321—Disposition
- H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/32245—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73251—Location after the connecting process on different surfaces
- H01L2224/73265—Layer and wire connectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/181—Encapsulation
Abstract
本發明提供一種導電性、接著性、作業性良好且可低價地製造之導電性樹脂組合物。導電性樹脂組合物含有(A)銀被覆二氧化矽粒子、(B)熱硬化性樹脂、及(C)硬化劑作為必需成分。(A)銀被覆二氧化矽粒子於導電性樹脂組合物中含有35~90質量%。又，(A)銀被覆二氧化矽粒子係縱橫比為1.0~1.2、比表面積為0.3~5.0m2/g、累積體積粒徑D50為1~10μm、累積體積粒徑D10、D50之比D50/D10為1.5~5.0、及最大粒徑為40μm以下之球狀粒子。 The present invention provides a conductive resin composition which has good conductivity, adhesion, and workability, and can be manufactured at low cost. The conductive resin composition contains (A) silver-coated silica particles, (B) a thermosetting resin, and (C) a hardener as essential components. (A) The silver-coated silicon dioxide particles are contained in the conductive resin composition in an amount of 35 to 90% by mass. (A) The silver-coated silicon dioxide particles have an aspect ratio of 1.0 to 1.2, a specific surface area of 0.3 to 5.0 m 2 / g, a cumulative volume particle diameter D 50 of 1 to 10 μm, and a cumulative volume particle diameter D 10 and D 50. Spherical particles having a ratio D 50 / D 10 of 1.5 to 5.0 and a maximum particle diameter of 40 μm or less.
Description
本發明係關於一種用以將半導體元件接著於支持構件所較佳使用之導電性樹脂組合物及使用其之半導體裝置。 The present invention relates to a conductive resin composition which is preferably used for bonding a semiconductor element to a supporting member and a semiconductor device using the same.
隨著高度資訊化社會之擴大及電子設備產業之顯著發展，電晶體、IC(Integrated Circuit，積體電路)、LSI(Large Scale Integration，大型積體電路)、LED(Light Emitting Diode，發光二極體)等半導體裝置所使用之半導體元件之積體度增加，對於半導體裝置要求散熱性、可靠性等之提昇。又，為了提高方便性、可攜性等，對於半導體裝置要求小型化及高性能化，對於用於半導體裝置之零件亦要求小型化及高性能化。例如，於半導體裝置中，將支持構件與半導體元件接著時使用導電性樹脂組合物。針對此種導電性樹脂組合物，要求導電性、接著性、作業性等基本特性，以及輕量化及低成本化。 With the expansion of a highly information-oriented society and the remarkable development of the electronic equipment industry, transistors, ICs (Integrated Circuits), LSIs (Large Scale Integration), and LEDs (Light Emitting Diodes) The volume of integrated semiconductor elements used in semiconductor devices such as semiconductor devices has increased, and semiconductor devices have been required to improve heat dissipation and reliability. Further, in order to improve convenience, portability, and the like, miniaturization and high performance of semiconductor devices are required, and miniaturization and high performance of components used for semiconductor devices are also required. For example, in a semiconductor device, a conductive resin composition is used when a support member is bonded to a semiconductor element. For such a conductive resin composition, basic characteristics such as conductivity, adhesiveness, workability, weight reduction, and cost reduction are required.
一般而言，於導電性樹脂組合物中，藉由填充銀粉作為導電粉末而表現導電性。然而，銀粉由於價格較高，故而就製造成本之觀點而言，較佳為控制使用。又，銀粉由於比重較大且為10.5，故而容易於導電性樹脂組合物中沈澱。因此，近年來，作為導電粉末，正研究使用包含銀以外之材料之粒子之表面被覆有銀等金屬之金屬被覆粉末。根據金屬被覆粉末，僅表面被銀等金屬所被覆，故而可謀求輕量化及低成本化。 In general, the conductive resin composition exhibits conductivity by being filled with silver powder as a conductive powder. However, since silver powder is relatively expensive, it is preferable to control the use from the viewpoint of manufacturing costs. In addition, since the silver powder has a large specific gravity of 10.5, it is easy to precipitate in the conductive resin composition. Therefore, in recent years, as a conductive powder, the use of a metal-coated powder in which the surface of particles containing a material other than silver is coated with a metal such as silver is being studied. According to the metal-coated powder, only the surface is covered with a metal such as silver, so that weight reduction and cost reduction can be achieved.
作為金屬被覆粉末，已知有於玻璃原料中添加金屬成分進行熔 融，並且於還原性氣氛中進行熱處理，而使金屬皮膜析出於表面者(例如參照專利文獻1)。然而，就此種金屬被覆粉末而言，金屬皮膜容易變得不均勻，粒徑亦容易變得不一致。因此，導電性樹脂組合物之作業性或導電性變差，又，於將支持構件與半導體元件接著時，半導體元件容易產生傾斜。 As a metal-coated powder, it is known to add a metal component to a glass raw material and melt it. Melting, and performing a heat treatment in a reducing atmosphere to precipitate a metal film on the surface (for example, refer to Patent Document 1). However, with such a metal-coated powder, the metal film tends to become non-uniform, and the particle diameter also tends to become non-uniform. Therefore, the workability or conductivity of the conductive resin composition is deteriorated, and when the supporting member is bonded to the semiconductor element, the semiconductor element is liable to be inclined.
又，作為金屬被覆粉末，已知有表面經銀被覆而成者(例如參照專利文獻2、3)。然而，該金屬被覆粉末係使用於導電圖案之形成等者，於導電性樹脂組合物中含有大量之有機溶劑。於將此種含有大量有機溶劑之導電性樹脂組合物使用於半導體元件之接著之情形時會產生空隙，故而無法獲得充分之接著性。 In addition, as the metal-coated powder, a surface coated with silver is known (for example, refer to Patent Documents 2 and 3). However, this metal-coated powder is used for forming a conductive pattern or the like, and contains a large amount of an organic solvent in the conductive resin composition. When such a conductive resin composition containing a large amount of an organic solvent is used for the bonding of a semiconductor device, voids are generated, so that sufficient adhesiveness cannot be obtained.
又，作為金屬被覆粉末，已知有利用銀被覆表面、且設為特定之縱橫比之薄片狀者(例如參照專利文獻4)。然而，於薄片狀之情形時，難以被覆角部，無法獲得充分之導電性。相對於此，藉由增多被覆量，亦可均勻地被覆，但金屬被覆粉末之比重容易變大。若金屬被覆粉末之比重變大，則導電性樹脂組合物之質量容易增加，且金屬被覆粉末容易於導電性樹脂組合物中沈澱。又，於薄片狀之情形時，被覆容易因略微之衝擊或應力等外部因素而剝離，導致無法獲得充分之導電性或接著性。進而，於薄片狀之情形時，由於斷裂時之龜裂容易延伸，故而無法獲得充分之接著性。 Further, as the metal-coated powder, a sheet having a specific aspect ratio with a silver-coated surface is known (for example, refer to Patent Document 4). However, in the case of a thin sheet, it is difficult to cover the corners, and sufficient conductivity cannot be obtained. On the other hand, it is possible to uniformly coat by increasing the amount of coating, but the specific gravity of the metal-coated powder tends to increase. When the specific gravity of the metal-coated powder becomes large, the mass of the conductive resin composition is likely to increase, and the metal-coated powder is liable to precipitate in the conductive resin composition. Moreover, in the case of a sheet, the coating is likely to be peeled off due to external factors such as slight impact or stress, resulting in failure to obtain sufficient conductivity or adhesiveness. Furthermore, in the case of a thin sheet, since cracks at the time of rupture easily extend, sufficient adhesion cannot be obtained.
[專利文獻1]日本專利特開昭51-053295號公報 [Patent Document 1] Japanese Patent Laid-Open No. 51-053295
[專利文獻2]日本專利特開2012-079457號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2012-079457
[專利文獻3]日本專利特表2010-539650號公報 [Patent Document 3] Japanese Patent Publication No. 2010-539650
[專利文獻4]國際公開第2012/118061號 [Patent Document 4] International Publication No. 2012/118061
本發明係應對此種課題而成者，目的在於提供一種導電性、接著性、作業性良好且可低價地製造之導電性樹脂組合物。又，本發明之目的在於提供一種使用有此種導電性樹脂組合物之可靠性優異之半導體裝置。 The present invention has been made in response to such a problem, and an object thereof is to provide a conductive resin composition which is excellent in conductivity, adhesion, workability, and can be manufactured at low cost. Another object of the present invention is to provide a semiconductor device having excellent reliability using such a conductive resin composition.
本發明之導電性樹脂組合物含有(A)銀被覆二氧化矽粒子、(B)熱硬化性樹脂、及(C)硬化劑作為必需成分。(A)銀被覆二氧化矽粒子於導電性樹脂組合物中含有35~90質量%。又，(A)銀被覆二氧化矽粒子係縱橫比為1.0~1.2、比表面積為0.3~5.0m2/g、累積體積粒徑D50為1~10μm、累積體積粒徑D10、D50之比D50/D10為1.5~5.0、及最大粒徑為40μm以下之球狀粒子。 The conductive resin composition of the present invention contains (A) silver-coated silica particles, (B) a thermosetting resin, and (C) a hardener as essential components. (A) The silver-coated silicon dioxide particles are contained in the conductive resin composition in an amount of 35 to 90% by mass. (A) The silver-coated silicon dioxide particles have an aspect ratio of 1.0 to 1.2, a specific surface area of 0.3 to 5.0 m 2 / g, a cumulative volume particle diameter D 50 of 1 to 10 μm, and a cumulative volume particle diameter D 10 and D 50. Spherical particles having a ratio D 50 / D 10 of 1.5 to 5.0 and a maximum particle diameter of 40 μm or less.
根據本發明，可提供一種導電性、接著性、作業性良好且可低價地製造之導電性樹脂組合物。又，根據本發明，藉由使用上述導電性樹脂組合物接著半導體元件，可提供一種可靠性優異之半導體裝置。 According to the present invention, it is possible to provide a conductive resin composition which is excellent in conductivity, adhesiveness, workability, and can be manufactured at low cost. Furthermore, according to the present invention, a semiconductor device having excellent reliability can be provided by bonding the semiconductor element using the conductive resin composition described above.
1‧‧‧半導體裝置 1‧‧‧ semiconductor device
2‧‧‧半導體元件 2‧‧‧Semiconductor
2a‧‧‧電極 2a‧‧‧electrode
3‧‧‧導電性樹脂組合物 3‧‧‧ conductive resin composition
4‧‧‧支持構件 4‧‧‧ supporting components
4a‧‧‧引線部 4a‧‧‧Leader
5‧‧‧接合線 5‧‧‧ bonding wire
6‧‧‧密封用樹脂組合物 6‧‧‧resin composition for sealing
圖1係表示一實施形態之半導體裝置之剖視圖。 FIG. 1 is a cross-sectional view showing a semiconductor device according to an embodiment.
以下，針對用以實施本發明之形態進行說明。 Hereinafter, the form for implementing this invention is demonstrated.
本發明之一實施形態之導電性樹脂組合物含有(A)銀被覆二氧化矽粒子、(B)熱硬化性樹脂、及(C)硬化劑作為必需成分。此種導電性樹脂組合物可較佳地使用於將半導體元件接著於支持構件。 The conductive resin composition according to an embodiment of the present invention contains (A) silver-coated silica particles, (B) a thermosetting resin, and (C) a hardener as essential components. Such a conductive resin composition can be preferably used for bonding a semiconductor element to a support member.
(A)成分之銀被覆二氧化矽粒子係二氧化矽粒子之表面經銀被覆而成者，且用於對導電性樹脂組合物賦予導電性。銀被覆二氧化矽粒 子係縱橫比為1.0~1.2、比表面積為0.3~5.0m2/g、累積體積粒徑D50為1~10μm、累積體積粒徑D10、D50之比D50/D10為1.5~5.0、及最大粒徑為40μm以下之球狀粒子。再者，銀被覆二氧化矽粒子可單獨使用1種，亦可混合2種以上而使用。又，比表面積係根據氣體吸附法而進行測定。又，銀被覆二氧化矽粒子之D10、D50、及最大粒徑係根據雷射繞射散射式粒度分佈測定法進行測定。 (A) Component silver-coated silicon dioxide particles are those in which the surface of the silicon dioxide particles is coated with silver, and are used to impart conductivity to the conductive resin composition. Silver-coated silicon dioxide particles based an aspect ratio of 1.0 to 1.2, a specific surface area of 0.3 ~ 5.0m 2 / g, a volume cumulative particle diameter D 50 of 1 ~ 10μm, the cumulative volume particle diameter D 10, D 50 of the ratio D 50 / D 10 is a spherical particle having a diameter of 1.5 to 5.0 and a maximum particle diameter of 40 μm or less. The silver-coated silicon dioxide particles may be used alone or in combination of two or more. The specific surface area is measured by a gas adsorption method. The D 10 , D 50 , and maximum particle size of the silver-coated silicon dioxide particles were measured by a laser diffraction scattering particle size distribution measurement method.
銀被覆二氧化矽粒子為球狀。於球狀之情形時，填充性、分散性、應力緩和性優異，故而較佳。再者，銀被覆二氧化矽粒子只要整體為球狀，則可為中空狀、多孔狀，亦可於表面具有多個突起或凹凸。 The silver-coated silica particles are spherical. In the case of a spherical shape, it is preferable because it has excellent filling properties, dispersibility, and stress relaxation properties. In addition, as long as the silver-coated silicon dioxide particles are spherical as a whole, they may be hollow or porous, and may have multiple protrusions or irregularities on the surface.
銀被覆二氧化矽粒子具有二氧化矽粒子作為芯材。二氧化矽粒子之形狀較佳為球狀。球狀之二氧化矽粒子例如係藉由使經熔融爐熔融之二氧化矽自上部落下，於冷卻時進行球狀化而製造。亦可於進行藉由銀之被覆之前對二氧化矽粒子實施表面處理。 The silver-coated silicon dioxide particles have silicon dioxide particles as a core material. The shape of the silica particles is preferably spherical. Spherical silicon dioxide particles are produced, for example, by spheroidizing silicon dioxide melted in a melting furnace from an upper tribe and cooling it. Surface treatment may also be performed on the silicon dioxide particles before coating with silver.
作為藉由銀被覆二氧化矽粒子之表面之方法，可列舉：蒸鍍法、濺鍍法、電鍍法、置換鍍敷法、無電解鍍敷法等。該等方法可組合進行。該等方法之中，就可均勻地被覆二氧化矽粒子之表面而言，較佳為無電解鍍敷法。作為具體之被覆之方法，例如可列舉藉由鈀進行活化而鍍鎳後，進行鍍銀之方法。根據此種方法，可有效率地被覆二氧化矽粒子之表面。 Examples of the method for coating the surface of the silicon dioxide particles with silver include a vapor deposition method, a sputtering method, a plating method, a displacement plating method, and an electroless plating method. These methods can be combined. Among these methods, an electroless plating method is preferred in terms of the surface on which the silica particles can be uniformly coated. As a specific coating method, for example, a method in which nickel is plated by activating with palladium, and then silver is plated. According to this method, the surface of the silicon dioxide particles can be efficiently covered.
於銀被覆二氧化矽粒子之縱橫比為1.0~1.2之情形時，可將銀被覆二氧化矽粒子高填充於導電性樹脂組合物中，藉此可使體積電阻率降低。又，於銀被覆二氧化矽粒子之縱橫比為1.0~1.2之情形時，即便於導電性樹脂組合物中之銀被覆二氧化矽粒子之含量較多之情形時，亦可抑制黏度之上升，從而作業性變得良好。再者，本說明書中之縱橫比係藉由(粒子之最大長徑/與最大長徑正交之寬度)而求出。 When the aspect ratio of the silver-coated silicon dioxide particles is 1.0 to 1.2, the conductive resin composition can be highly filled with the silver-coated silicon dioxide particles, thereby reducing the volume resistivity. In addition, when the aspect ratio of the silver-coated silicon dioxide particles is 1.0 to 1.2, even when the content of the silver-coated silicon dioxide particles in the conductive resin composition is large, an increase in viscosity can be suppressed. As a result, workability is improved. In addition, the aspect ratio in this specification is calculated | required by (the maximum long diameter of a particle / the width orthogonal to a maximum long diameter).
於銀被覆二氧化矽粒子之比表面積為0.3~5.0m2/g之情形時，導電性樹脂組合物之作業性變得良好，且體積電阻率亦降低。即，於比表面積為0.3m2/g以上之情形時，作業性變得良好。例如，即便於利用針徑0.3mm之注射器進行分注之情形時，亦可抑制滴液或拉絲，從而作業性變得良好。於比表面積為5.0m2/g以下之情形時，黏度、觸變性降低，作業性變得良好。又，於比表面積為5.0m2/g以下之情形時，由於可相對於二氧化矽粒子之量減少被覆二氧化矽粒子之銀之量，故而可減小銀被覆二氧化矽粒子之比重，從而可抑制銀被覆二氧化矽粒子之沈澱。又，於比表面積為5.0m2/g以下之情形時，只要銀之量相同，則被覆面積變小，故而銀之被覆容易變厚，藉此可降低體積電阻率。再者，比表面積係根據氣體吸附法進行測定。 When the specific surface area of the silver-coated silicon dioxide particles is 0.3 to 5.0 m 2 / g, the workability of the conductive resin composition becomes good, and the volume resistivity also decreases. That is, when the specific surface area is 0.3 m 2 / g or more, the workability becomes good. For example, even when dispensing is performed using a syringe having a needle diameter of 0.3 mm, dripping or stringing can be suppressed, and workability is improved. When the specific surface area is 5.0 m 2 / g or less, viscosity and thixotropy are reduced, and workability is improved. In addition, when the specific surface area is 5.0 m 2 / g or less, the amount of silver coated with the silicon dioxide particles can be reduced relative to the amount of the silicon dioxide particles, so the specific gravity of the silver-coated silicon dioxide particles can be reduced. As a result, precipitation of silver-coated silicon dioxide particles can be suppressed. In addition, when the specific surface area is 5.0 m 2 / g or less, as long as the amount of silver is the same, the coating area becomes small, so that the coating of silver is likely to be thickened, thereby reducing the volume resistivity. The specific surface area is measured by a gas adsorption method.
於銀被覆二氧化矽粒子之D50為1~10μm之情形時，導電性樹脂組合物之作業性變得良好。即，於D50為1μm以上之情形時，導電性樹脂組合物之黏度降低，故而作業性變得良好。於D50為10μm以下之情形時，例如即便於利用針徑0.3mm之注射器進行分注之情形時，亦可抑制注射器頂端之噴嘴堵塞，而不易產生塗佈不良，從而作業性變得良好。 When the D 50 of the silver-coated silicon dioxide particles is 1 to 10 μm, the workability of the conductive resin composition becomes good. That is, when D 50 is 1 μm or more, the viscosity of the conductive resin composition is reduced, and thus the workability is improved. When the D 50 is 10 μm or less, for example, even when dispensing is performed with a syringe having a needle diameter of 0.3 mm, clogging of the nozzle at the tip of the syringe can be suppressed, and coating failure is less likely to occur, thereby improving workability.
於銀被覆二氧化矽粒子之比D50/D10為1.5~5.0之情形時，導電性樹脂組合物之導電性或接著性變得良好。例如，於比D50/D10為5.0以下之情形時，由於細粉之比率較低，故而應由銀被覆之面積變小。藉此，容易增厚銀之被覆，從而容易使體積電阻率降低。又，於比D50/D10為5.0以下之情形時，由於細粉之比率較低，故而銀被覆二氧化矽粒子之被覆所利用之熱硬化性樹脂之量變少，故而於支持構件與導電性樹脂組合物之界面、半導體元件與導電性樹脂組合物之界面處之熱硬化性樹脂之量增加，從而接著性變得良好。 When the ratio D 50 / D 10 of the silver-coated silicon dioxide particles is 1.5 to 5.0, the conductivity or adhesiveness of the conductive resin composition becomes good. For example, when the ratio D 50 / D 10 is 5.0 or less, the ratio of fine powder is low, so the area to be covered with silver becomes small. This makes it easy to thicken the coating of silver, and it is easy to reduce the volume resistivity. When the ratio D 50 / D 10 is 5.0 or less, the ratio of fine powder is low, so that the amount of the thermosetting resin used for the coating of the silver-coated silicon dioxide particles is reduced. The amount of the thermosetting resin at the interface between the conductive resin composition and the interface between the semiconductor element and the conductive resin composition increases, so that the adhesiveness becomes good.
於銀被覆二氧化矽粒子之最大粒徑為40μm以下之情形時，可抑 制在將半導體元件與支持構件接著時之半導體元件之傾斜。例如，於將半導體元件與支持構件經由導電性樹脂組合物進行接著之情形時，半導體元件與支持構件之間之導電性樹脂組合物之厚度變為10~30μm。此時，若存在如粒徑超過40μm之銀被覆二氧化矽粒子，則半導體元件容易傾斜。又，於銀被覆二氧化矽粒子之最大粒徑為40μm以下之情形時，即便利用針徑0.3mm之注射器進行分注，亦可抑制注射器頂端之噴嘴堵塞。 When the maximum particle size of the silver-coated silicon dioxide particles is 40 μm or less, The inclination of the semiconductor element when the semiconductor element is attached to the supporting member is controlled. For example, when a semiconductor element and a support member are bonded via a conductive resin composition, the thickness of the conductive resin composition between the semiconductor element and the support member becomes 10 to 30 μm. At this time, if there are silver-coated silicon dioxide particles having a particle diameter of more than 40 μm, the semiconductor element is easily inclined. In addition, when the maximum particle diameter of the silver-coated silicon dioxide particles is 40 μm or less, even if a syringe with a needle diameter of 0.3 mm is used for dispensing, clogging of the nozzle at the tip of the syringe can be suppressed.
銀被覆二氧化矽粒子之比重較佳為2.4~3.6。於比重為2.4~3.6之情形時，導電性樹脂組合物之分散性或導電性變得良好。即，於比重為2.4以上之情形時，銀被覆二氧化矽粒子之銀之被覆容易變成充分之厚度，藉此導電性樹脂組合物之導電性容易變得良好。於比重為3.6以下之情形時，可抑制導電性樹脂組合物中之銀被覆二氧化矽粒子之沈澱，從而成為均勻地分散有銀被覆二氧化矽粒子者。比重更佳為2.7~3.3。 The specific gravity of the silver-coated silicon dioxide particles is preferably 2.4 to 3.6. When the specific gravity is 2.4 to 3.6, the dispersibility or conductivity of the conductive resin composition becomes good. That is, when the specific gravity is 2.4 or more, the silver coating of the silver-coated silicon dioxide particles is likely to have a sufficient thickness, whereby the conductivity of the conductive resin composition is easily improved. When the specific gravity is 3.6 or less, precipitation of the silver-coated silicon dioxide particles in the conductive resin composition can be suppressed, and the silver-coated silicon dioxide particles can be uniformly dispersed. The better specific gravity is 2.7 ~ 3.3.
銀被覆二氧化矽粒子之表面較佳為經矽烷偶合劑被覆。於銀被覆二氧化矽粒子之表面經矽烷偶合劑被覆之情形時，銀被覆二氧化矽粒子與熱硬化性樹脂之密接性或相溶性提昇，從而導電性樹脂組合物之接著性變得良好。 The surface of the silver-coated silica particles is preferably coated with a silane coupling agent. When the surface of the silver-coated silicon dioxide particles is coated with a silane coupling agent, the adhesion or compatibility between the silver-coated silicon dioxide particles and the thermosetting resin is improved, and the adhesiveness of the conductive resin composition becomes good.
於藉由矽烷偶合劑被覆銀被覆二氧化矽粒子之表面之情形時，較佳為利用脂肪酸或脂肪酸鹽對銀被覆二氧化矽粒子之表面進行處理之後，利用矽烷偶合劑對最表面進行處理。以此方式利用脂肪酸或脂肪酸鹽進行處理之後，藉由矽烷偶合劑進行處理，藉此使銀被覆二氧化矽粒子與熱硬化性樹脂之密接性或相溶性提昇，從而導電性樹脂組合物之接著性變得良好。 In the case where the surface of the silica-coated silicon dioxide particles is covered with a silane coupling agent, it is preferred that the surface of the silver-coated silica particles is treated with a fatty acid or a fatty acid salt, and then the outermost surface is treated with the silane coupling agent. After treatment with fatty acids or fatty acid salts in this manner, treatment with a silane coupling agent improves adhesion or compatibility between the silver-coated silicon dioxide particles and the thermosetting resin, thereby adhering the conductive resin composition. Sex becomes good.
作為藉由矽烷偶合劑之被覆之方法，為濕式法、乾式法之任一者皆可。例如可列舉：向利用銀被覆二氧化矽粒子之表面時之鍍敷液 中添加矽烷偶合劑之方法；根據氣相反應，對銀被覆二氧化矽粒子之表面被覆矽烷偶合劑之方法；將銀被覆二氧化矽粒子浸漬於在醇、石油系溶劑等溶劑中添加有矽烷偶合劑之溶液中之方法；將上述溶液噴霧至銀被覆二氧化矽粒子之方法等。 As a method of coating with a silane coupling agent, either a wet method or a dry method may be used. For example, a plating solution for coating the surface of silicon dioxide particles with silver A method for adding a silane coupling agent to a surface; a method for coating a surface of a silver-coated silicon dioxide particle with a silane coupling agent based on a gas-phase reaction; immersing a silver-coated silicon dioxide particle in a solvent such as an alcohol or a petroleum-based solvent to add a silane A method of a coupling agent solution; a method of spraying the above solution onto silver-coated silicon dioxide particles, and the like.
作為矽烷偶合劑，可列舉：3-縮水甘油氧基丙基甲基二甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三乙氧基矽烷、3-三乙氧基矽烷基-N-(1,3-二甲基-亞丁基)丙基胺、3-巰基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、甲基三甲氧基矽烷、雙(三乙氧基矽烷基丙基)四硫醚等。該等矽烷偶合劑可單獨使用1種，亦可混合2種以上而使用。就與熱硬化性樹脂、特別是與環氧樹脂之相溶性或反應性之觀點而言，較佳為3-縮水甘油氧基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、甲基三甲氧基矽烷、雙(三乙氧基矽烷基丙基)四硫醚。 Examples of the silane coupling agent include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldiethoxy Silane, 3-glycidyloxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl ) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-triethoxysilane-N- (1 , 3-dimethyl-butylene) propylamine, 3-mercaptopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxy Ethoxysilane, methyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide and the like. These silane coupling agents may be used singly or in combination of two or more kinds. From the viewpoint of compatibility or reactivity with a thermosetting resin, particularly with an epoxy resin, preferred are 3-glycidyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, methyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide.
銀被覆二氧化矽粒子之表面亦可藉由脂肪酸或脂肪酸鹽進行被覆而代替藉由矽烷偶合劑進行被覆。於銀被覆二氧化矽粒子之表面經脂肪酸或脂肪酸鹽被覆之情形時，銀被覆二氧化矽粒子之分散性或相溶性提昇，又，抑制銀被覆二氧化矽粒子彼此之凝聚。藉此，導電性樹脂組合物之接著性變得良好。 The surface of the silver-coated silicon dioxide particles may be coated with a fatty acid or a fatty acid salt instead of being coated with a silane coupling agent. When the surface of the silver-coated silica particles is coated with fatty acids or fatty acid salts, the dispersibility or compatibility of the silver-coated silica particles is improved, and the silver-coated silica particles are inhibited from agglomerating with each other. Thereby, the adhesiveness of a conductive resin composition becomes favorable.
作為藉由脂肪酸或脂肪酸鹽之被覆之方法，為濕式法、乾式法之任一者皆可。例如可列舉：向利用銀被覆二氧化矽粒子之表面時之鍍敷液中添加脂肪酸或脂肪酸鹽之方法；根據氣相反應，對銀被覆二氧化矽粒子之表面被覆脂肪酸或脂肪酸鹽之方法；將銀被覆二氧化矽 粒子浸漬於在醇、石油系溶劑等溶劑中添加有脂肪酸或脂肪酸鹽之溶液中之方法；將上述溶液噴霧至銀被覆二氧化矽粒子之方法等。 As a method of coating with a fatty acid or a fatty acid salt, any of a wet method and a dry method may be used. For example, a method of adding a fatty acid or a fatty acid salt to the plating solution when the surface of the silicon dioxide particle is coated with silver; a method of coating a surface of the silver coated silicon dioxide particle with a fatty acid or a fatty acid salt according to a gas phase reaction; Silver-coated silicon dioxide A method in which particles are immersed in a solution in which a fatty acid or a fatty acid salt is added to a solvent such as an alcohol or a petroleum-based solvent; a method in which the solution is sprayed onto silver-coated silicon dioxide particles;
作為脂肪酸或脂肪酸鹽，可列舉：月桂酸、肉豆蔻酸、棕櫚酸、棕櫚油酸、珠光子酸、硬脂酸、油酸、亞麻油酸、次亞麻油酸、花生酸、花生四烯酸、山萮酸、丙酸、辛酸、丙烯酸、苯并***、及該等之鹽等。該等脂肪酸或脂肪酸鹽可單獨使用1種，亦可混合2種以上而使用。該等之中，就與熱硬化性樹脂之相溶性、導電性樹脂組合物之作業性之觀點而言，較佳為使用選自肉豆蔻酸、油酸、硬脂酸、及棕櫚酸中之至少1種。特別是就與環氧樹脂之相溶性等觀點而言，較佳為使用肉豆蔻酸。 Examples of fatty acids or fatty acid salts include lauric acid, myristic acid, palmitic acid, palmitoleic acid, pearlic acid, stearic acid, oleic acid, linoleic acid, hypolinolenic acid, arachidic acid, and arachidonic acid , Behenic acid, propionic acid, caprylic acid, acrylic acid, benzotriazole, and salts thereof. These fatty acids or fatty acid salts may be used singly or in combination of two or more kinds. Among these, from the viewpoints of compatibility with the thermosetting resin and workability of the conductive resin composition, it is preferable to use one selected from the group consisting of myristic acid, oleic acid, stearic acid, and palmitic acid. At least one. In particular, from the viewpoint of compatibility with epoxy resins, myristic acid is preferably used.
銀被覆二氧化矽粒子之含量於導電性樹脂組合物中為35~90質量%。於銀被覆二氧化矽粒子之含量為35~90質量%之情形時，導電性樹脂組合物之導電性、接著性、作業性變得良好。即，於銀被覆二氧化矽粒子之含量為35質量%以上之情形時，導電性樹脂組合物之導電性變得良好。又，於銀被覆二氧化矽粒子之含量為90質量%以下之情形時，導電性樹脂組合物之接著性或作業性變得良好，導電性樹脂組合物之製造成本亦降低。銀被覆二氧化矽粒子之含量較佳為40~80質量%。 The content of the silver-coated silicon dioxide particles in the conductive resin composition is 35 to 90% by mass. When the content of the silver-coated silicon dioxide particles is 35 to 90% by mass, the conductivity, adhesiveness, and workability of the conductive resin composition become good. That is, when the content of the silver-coated silicon dioxide particles is 35% by mass or more, the conductivity of the conductive resin composition becomes good. When the content of the silver-coated silicon dioxide particles is 90% by mass or less, the adhesiveness or workability of the conductive resin composition is improved, and the manufacturing cost of the conductive resin composition is also reduced. The content of the silver-coated silicon dioxide particles is preferably 40 to 80% by mass.
導電性樹脂組合物亦可含有銀被覆二氧化矽粒子、以及銀被覆二氧化矽粒子以外之填充材。作為銀被覆二氧化矽粒子以外之填充材，為導電性粒子、非導電性粒子之任一者皆可。 The conductive resin composition may contain fillers other than the silver-coated silicon dioxide particles and the silver-coated silicon dioxide particles. The filler other than the silver-coated silicon dioxide particles may be any of conductive particles and non-conductive particles.
作為導電性樹脂組合物所含有之導電性粒子，可列舉：銀粒子、銅粒子、鎳粒子、鋁粒子、銀被覆銅粒子、奈米銀粒子等。該等之中，就導電性、作業性之觀點而言，較佳為銀粒子、奈米銀粒子。奈米銀粒子由於會使高溫下之接著性提昇，故而尤佳。 Examples of the conductive particles contained in the conductive resin composition include silver particles, copper particles, nickel particles, aluminum particles, silver-coated copper particles, nano-silver particles, and the like. Among these, silver particles and nano silver particles are preferred from the viewpoints of conductivity and workability. Nano-silver particles are particularly preferred because they improve adhesion at high temperatures.
銀粒子之D50較佳為0.5~15μm。銀粒子之形狀較佳為薄片狀或 不定形狀。於D50為0.5~15μm、且形狀為薄片狀或不定形狀之情形時，導電性樹脂組合物之體積電阻率會降低，故而較佳。 The D 50 of the silver particles is preferably 0.5 to 15 μm. The shape of the silver particles is preferably flaky or irregular. In the case where D 50 is 0.5 to 15 μm and the shape is a sheet shape or an indefinite shape, the volume resistivity of the conductive resin composition is reduced, which is preferable.
奈米銀粒子之D50較佳為5~300nm。奈米銀粒子之形狀可列舉：薄片狀、鱗片狀、樹枝狀、棒狀、線狀、球狀、板型等，較佳為球狀或板型，更佳為板型。於板型之情形時，與球狀相比，使高溫下之接著性提昇之效果較大。又，於板型之情形時，除具有使高溫下之接著性提昇之效果以外，亦具有使常溫下之接著性提昇之效果。較佳為於奈米銀粒子之表面設置包含含有胺基、羧基等官能基之有機化合物之被覆層。 The D 50 of the nano silver particles is preferably 5 to 300 nm. Examples of the shape of the nano-silver particles include flaky, scaly, dendritic, rod-like, linear, spherical, and plate-shaped, and the like is preferably spherical or plate-shaped, and more preferably plate-shaped. In the case of a plate type, compared with a spherical shape, the effect of improving the adhesion at high temperature is greater. In addition, in the case of a plate type, in addition to the effect of improving the adhesiveness at high temperature, it also has the effect of improving the adhesiveness at normal temperature. It is preferable to provide a coating layer containing an organic compound containing a functional group such as an amine group and a carboxyl group on the surface of the nano silver particles.
與球狀奈米銀粒子不同，板型奈米銀粒子係使一金屬結晶面較大地成長而成者，且為具有均勻厚度之薄片狀之粒子。作為板型奈米銀粒子，可使用公知者。一般而言，板型奈米銀粒子之厚度為數奈米左右，大小為微米級。板型奈米銀粒子之形狀可列舉：三角形板狀、六角形板狀、切頂三角形板狀等。板型奈米銀粒子之表面較佳為被[111]面廣泛地覆蓋。板型奈米銀粒子之D50較佳為0.3~15μm。 Unlike spherical nano-silver particles, plate-type nano-silver particles are formed by growing a large metal crystal surface, and are flaky particles having a uniform thickness. As the plate-type nano silver particles, a known one can be used. Generally speaking, the thickness of plate-type nano-silver particles is about several nanometers and the size is in the order of micrometers. Examples of the shape of the plate-shaped nano-silver particles include a triangular plate shape, a hexagonal plate shape, and a cut-top triangular plate shape. The surface of the plate-shaped nano-silver particles is preferably widely covered with the [111] plane. The D 50 of the plate-shaped nano silver particles is preferably 0.3 to 15 μm.
板型奈米銀粒子之面方向上之長邊長度較佳為相對於厚度為8~150倍，更佳為10~50倍。又，板型奈米銀粒子之面方向上之短邊長度較佳為相對於厚度為1~100倍，更佳為3~50倍。於面方向上之長度為上述範圍內之情形時，板型奈米銀粒子容易於水平方向配向，形成更多接點，從而導電性變得良好，故而較佳。再者，所謂面方向，意指相對於厚度方向垂直之方向。 The length of the long side in the plane direction of the plate-shaped nano-silver particles is preferably 8 to 150 times, and more preferably 10 to 50 times the thickness. The short side length in the plane direction of the plate-shaped nano-silver particles is preferably 1 to 100 times, and more preferably 3 to 50 times, the thickness. In the case where the length in the plane direction is within the above range, the plate-type nano-silver particles are easily aligned in the horizontal direction, forming more contacts, so that the conductivity becomes good, which is preferable. The plane direction means a direction perpendicular to the thickness direction.
作為板型奈米銀粒子，可使用市售品。作為此種市售品，可列舉：TOKUSEN KOGYO股份有限公司製造之M612(商品名，D50：6~12μm，粒子厚度：60~100nm，熔點：250℃)、M27(商品名，D50：2~7μm，粒子厚度：60~100nm，熔點：200℃)、M13(商品名，D50：1~3μm，粒子厚度：40~60nm，熔點：200℃)、N300(商品 名，D50：0.3~0.6μm，粒子厚度：50nm以下，熔點：150℃)、MITSUBOSHI BELTING股份有限公司製造，MDot(商品名，D50：50nm)、Ag nano Powder-1(比表面積15~20mm2/g，≧95wt%)、Ag nano Powder-2(比表面積5~8mm2/g，≧98wt%)等。 As the plate-type nano silver particles, a commercially available product can be used. Examples of such commercially available products include M612 (trade name, D 50 : 6 to 12 μm, particle thickness: 60 to 100 nm, melting point: 250 ° C.), M27 (trade name, D 50 :) manufactured by TOKUSEN KOGYO Co., Ltd. 2 to 7 μm, particle thickness: 60 to 100 nm, melting point: 200 ° C.), M13 (trade name, D 50 : 1 to 3 μm, particle thickness: 40 to 60 nm, melting point: 200 ° C.), N300 (trade name, D 50 : 0.3 ~ 0.6μm, particle thickness: 50nm or less, melting point: 150 ℃), MITSUBOSHI BELTING manufacturing Co., MDOT (trade name, D 50: 50nm), Ag nano Powder-1 ( specific surface area of 15 ~ 20mm 2 / g, ≧ 95wt%), Ag nano Powder-2 (specific surface area: 5 ~ 8mm 2 / g, ≧ 98wt%), etc.
於含有導電性粒子(除銀被覆二氧化矽粒子以外)之情形時，其含量於銀被覆二氧化矽粒子及導電性粒子之合計中較佳為50質量%以下，更佳為30質量%以下。又，於含有導電性粒子之情形時，其含量就獲得充分之效果之觀點而言，於銀被覆二氧化矽粒子及導電性粒子之合計中較佳為1質量%以上，更佳為5質量%以上。 When the conductive particles (other than the silver-coated silicon dioxide particles) are contained, the content is preferably 50% by mass or less, and more preferably 30% by mass or less in the total of the silver-coated silicon dioxide particles and the conductive particles. . When the conductive particles are contained, the content is preferably 1% by mass or more, and more preferably 5% by mass from the viewpoint of obtaining a sufficient effect of the silver-coated silicon dioxide particles and the conductive particles. %the above.
作為導電性樹脂組合物所含有之非導電性粒子，為無機粒子、有機粒子之任一者皆可。 The non-conductive particles contained in the conductive resin composition may be either inorganic particles or organic particles.
作為導電性樹脂組合物所含有之無機粒子，可列舉：二氧化矽、煙霧狀二氧化矽、氧化鋁、氮化硼、氧化鈦、鋇、滑石、碳酸鈣、氫氧化鋁等。該等之中，就導電性樹脂組合物之作業性或接著性之觀點而言，較佳為二氧化矽或煙霧狀二氧化矽。二氧化矽之D50較佳為0.5~15μm。二氧化矽之形狀較佳為球狀。煙霧狀二氧化矽之一次粒徑D50較佳為5~300nm。煙霧狀二氧化矽之形狀並無特別限制。於含有煙霧狀二氧化矽之情形時，作業性會提昇，故而較佳。 Examples of the inorganic particles contained in the conductive resin composition include silica, fumed silica, alumina, boron nitride, titanium oxide, barium, talc, calcium carbonate, and aluminum hydroxide. Among these, in terms of workability or adhesiveness of the conductive resin composition, silicon dioxide or aerosol-like silicon dioxide is preferred. The D 50 of the silicon dioxide is preferably 0.5 to 15 μm. The shape of the silicon dioxide is preferably spherical. The primary particle diameter D 50 of the fumed silica is preferably 5 to 300 nm. The shape of the fumed silica is not particularly limited. In the case of containing fumed silica, the workability is improved, so it is better.
作為導電性樹脂組合物所含有之有機粒子，可列舉聚矽氧粉末、交聯聚合物等樹脂粒子。作為樹脂粒子之形狀，可列舉球狀、不定形狀等，就分散性之觀點而言，較佳為球狀。 Examples of the organic particles contained in the conductive resin composition include resin particles such as a polysiloxane powder and a crosslinked polymer. Examples of the shape of the resin particles include a spherical shape and an irregular shape. From the viewpoint of dispersibility, a spherical shape is preferred.
作為聚矽氧粉末，可列舉：具有交聯有直鏈狀二甲基聚矽氧烷而成之結構之聚矽氧橡膠粉末、作為具有矽氧烷鍵呈三次元網狀交聯而成之結構之聚有機倍半矽氧烷硬化物的聚矽氧樹脂粉末、聚矽氧橡膠粒子之表面經聚矽氧樹脂覆膜而成之聚矽氧複合粉末等。該等之中，就耐熱性及分散性之觀點而言，較佳為聚矽氧樹脂粉末、聚矽氧 複合粉末。 Examples of the polysiloxane powder include a polysiloxane rubber powder having a structure in which a linear dimethylpolysiloxane is crosslinked, and a polysiloxane powder having a three-dimensional network crosslink with a siloxane bond. Structured polyorganosilsesquioxane hardened polysiloxane resin powder, polysiloxane composite powder with polysiloxane coating on the surface of polysiloxane rubber particles. Among these, from the viewpoints of heat resistance and dispersibility, polysiloxane resin powder and polysiloxane are preferred. Composite powder.
作為聚矽氧粉末，可使用市售品。作為此種市售品，可列舉：信越化學工業公司製造之聚矽氧複合粉末(KMP-600、KMP-601、KMP-602、KMP-605、X-52-7030等)、聚矽氧橡膠粉末(KMP-597、KMP-598、KMP-594、X-52-875等)、聚矽氧樹脂粉末(KMP-590、KMP-701、X-52-854、X-52-1621等)。該等聚矽氧粉末可單獨使用1種，亦可混合2種以上而使用。 As the polysiloxane powder, a commercially available product can be used. Examples of such commercially available products include polysiloxane composite powders (KMP-600, KMP-601, KMP-602, KMP-605, X-52-7030, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., and silicone rubber Powder (KMP-597, KMP-598, KMP-594, X-52-875, etc.), silicone resin powder (KMP-590, KMP-701, X-52-854, X-52-1621, etc.). These polysiloxane powders can be used singly or in combination of two or more kinds.
作為交聯聚合物，可列舉：二乙烯苯交聯聚合物、甲基丙烯酸甲酯樹脂(PMMA)、甲基丙烯酸乙酯樹脂(PEMA)、甲基丙烯酸丁酯樹脂(PBMA)、甲基丙烯酸甲酯-甲基丙烯酸乙酯共聚物及該等之混合物等。該等之中，就耐熱性、穩定性優異之方面而言，較佳為二乙烯苯交聯聚合物、甲基丙烯酸甲酯樹脂。 Examples of the crosslinked polymer include divinylbenzene crosslinked polymer, methyl methacrylate resin (PMMA), ethyl methacrylate resin (PEMA), butyl methacrylate resin (PBMA), and methacrylic acid. Methyl-ethyl methacrylate copolymers and mixtures thereof. Among these, a divinylbenzene crosslinked polymer and a methyl methacrylate resin are preferable at the point which is excellent in heat resistance and stability.
有機粒子之平均粒徑較佳為0.5~40μm。於有機粒子之平均粒徑為0.5~40μm之情形時，導電性樹脂組合物之應力得到緩和，耐回焊性、耐熱衝擊性等變得良好。有機粒子之平均粒徑更佳為0.8~20μm，進而較佳為0.8~10μm，尤佳為0.8~5μm。 The average particle diameter of the organic particles is preferably 0.5 to 40 μm. When the average particle diameter of the organic particles is 0.5 to 40 μm, the stress of the conductive resin composition is relaxed, and reflow resistance, thermal shock resistance, and the like are improved. The average particle diameter of the organic particles is more preferably 0.8 to 20 μm, more preferably 0.8 to 10 μm, and even more preferably 0.8 to 5 μm.
再者，亦可於上述無機粒子及有機粒子之表面被覆金、銀等金屬，而用作導電性粒子。 Furthermore, the surfaces of the inorganic particles and organic particles may be coated with a metal such as gold or silver, and used as conductive particles.
於含有非導電性粒子之情形時，其含量於全部填充材中較佳為50質量%以下，更佳為30質量%以下。此處，所謂填充材，意指銀被覆二氧化矽粒子、導電性粒子、及非導電性粒子。又，於含有非導電性粒子之情形時，其含量就獲得充分之效果之觀點而言，於全部填充材中較佳為1質量%以上，更佳為3質量%以上。 When the non-conductive particles are contained, the content is preferably 50% by mass or less, and more preferably 30% by mass or less in the entire filler. Here, the filler means silver-coated silicon dioxide particles, conductive particles, and non-conductive particles. When the non-conductive particles are contained, the content is preferably 1% by mass or more, and more preferably 3% by mass or more, in terms of obtaining a sufficient effect.
作為(B)成分之熱硬化性樹脂，可較佳地使用利用於接著用途等者。熱硬化性樹脂較佳為於常溫(25℃)下為液狀。作為熱硬化性樹脂，可列舉：環氧樹脂、酚樹脂、不飽和聚酯樹脂、聚醯亞胺樹脂、 聚矽氧樹脂、聚胺基甲酸酯樹脂、二甲苯樹脂、丁二烯樹脂、順丁烯二醯亞胺樹脂、氰酸酯樹脂、自由基聚合性丙烯酸系樹脂等。該等熱硬化性樹脂可單獨使用1種，亦可混合2種以上而使用。該等之中，較佳為含有選自環氧樹脂、丙烯酸系樹脂、及順丁烯二醯亞胺樹脂中之至少1種。 As the thermosetting resin as the component (B), it can be preferably used for adhesive applications and the like. The thermosetting resin is preferably liquid at normal temperature (25 ° C). Examples of the thermosetting resin include epoxy resin, phenol resin, unsaturated polyester resin, polyimide resin, Polysiloxane resin, polyurethane resin, xylene resin, butadiene resin, maleimide resin, cyanate resin, radical polymerizable acrylic resin, and the like. These thermosetting resins may be used alone or in combination of two or more. Among these, it is preferable to contain at least one selected from the group consisting of an epoxy resin, an acrylic resin, and a maleimide resin.
作為環氧樹脂，可使用1分子中具有2個以上縮水甘油基者。作為此種環氧樹脂，可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、聯苯型環氧樹脂、酚醛清漆型環氧樹脂、醚或聚醚型環氧樹脂、酯或聚酯環氧樹脂、胺基甲酸酯型環氧樹脂、多官能型環氧樹脂、脂環式環氧樹脂、脂肪族環氧樹脂、氫化型環氧樹脂、萘型環氧樹脂、茀型環氧樹脂、環氧乙烷改性雙酚A型環氧樹脂、環氧丙烷改性雙酚A型環氧樹脂、縮水甘油基改性聚丁二烯樹脂、縮水甘油基改性三樹脂、聚矽氧改性環氧樹脂、胺基苯酚型環氧樹脂、可撓性環氧樹脂、甲基丙烯酸改性環氧樹脂、丙烯酸改性環氧樹脂、特殊改性環氧樹脂、二環戊二烯型環氧樹脂、側鏈羥基烷基改性環氧樹脂、長鏈烷基改性環氧樹脂、醯亞胺改性環氧樹脂、CTBN(carboxyl terminated butadiene-acrylonitrile，羧基封端之聚丁二烯丙烯腈)改性環氧樹脂等。再者，環氧樹脂並不限定於該等者。 As the epoxy resin, one having two or more glycidyl groups in one molecule can be used. Examples of such epoxy resins include bisphenol A epoxy resin, bisphenol F epoxy resin, biphenyl epoxy resin, novolac epoxy resin, ether or polyether epoxy resin, and esters. Or polyester epoxy resin, urethane epoxy resin, multifunctional epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, hydrogenated epoxy resin, naphthalene epoxy resin, Epoxy resin, ethylene oxide modified bisphenol A epoxy resin, propylene oxide modified bisphenol A epoxy resin, glycidyl modified polybutadiene resin, glycidyl modified three Resin, polysiloxane modified epoxy resin, aminophenol type epoxy resin, flexible epoxy resin, methacrylic acid modified epoxy resin, acrylic acid modified epoxy resin, special modified epoxy resin, two Cyclopentadiene epoxy resin, side chain hydroxyalkyl modified epoxy resin, long chain alkyl modified epoxy resin, fluorene imine modified epoxy resin, CTBN (carboxyl terminated butadiene-acrylonitrile, carboxyl terminated Polybutadiene acrylonitrile) modified epoxy resin. Moreover, epoxy resin is not limited to these.
環氧樹脂較佳為於常溫下為液狀。再者，於常溫下為固體狀之環氧樹脂亦可藉由利用液狀環氧樹脂、反應性稀釋劑、溶劑等進行稀釋，製成液狀而使用。作為液狀環氧樹脂，較佳為雙酚A型環氧樹脂、雙酚F型環氧樹脂、1,6-己二醇二縮水甘油醚、4,4'-亞異丙基二環己醇二縮水甘油醚、1,4-環己烷二甲醇二縮水甘油醚、1,4-丁二醇二縮水甘油醚、可撓性環氧樹脂。該等之中，就獲得良好之接著強度而言，較佳為可撓性環氧樹脂。 The epoxy resin is preferably liquid at normal temperature. Furthermore, an epoxy resin that is solid at normal temperature can be used in a liquid state by diluting it with a liquid epoxy resin, a reactive diluent, a solvent, or the like. As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, 1,6-hexanediol diglycidyl ether, and 4,4'-isopropylidene dicyclohexyl are preferable. Glycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,4-butanediol diglycidyl ether, flexible epoxy resin. Among these, a flexible epoxy resin is preferable in order to obtain favorable adhesive strength.
作為可撓性環氧樹脂，可列舉：聚乙二醇之二縮水甘油醚、聚 丙二醇之二縮水甘油醚、包含含有碳數2~9(較佳為2~4)之伸烷基之聚氧伸烷基二醇或聚四亞甲基醚二醇等的長鏈多元醇之聚縮水甘油醚；將(甲基)丙烯酸縮水甘油酯與乙烯、乙酸乙烯酯或(甲基)丙烯酸酯等自由基聚合性單體之共聚物、共軛二烯化合物之(共)聚合物或其部分氫化物之(共)聚合物中之不飽和碳鍵進行環氧化而成者；具有環氧基之聚酯樹脂、導入有胺基甲酸酯鍵或聚己內酯鍵之胺基甲酸酯改性環氧樹脂或聚己內酯改性環氧樹脂；二聚酸或其衍生物之分子內導入有環氧基之二聚酸改性環氧樹脂；NBR(butadiene-acrylonitrile rubber，丁二烯-丙烯腈橡膠)、CTBN、聚丁二烯、丙烯酸系橡膠等橡膠成分之分子內導入有環氧基之橡膠改性環氧樹脂等。 Examples of the flexible epoxy resin include diglycidyl ether of polyethylene glycol, and poly (ethylene glycol). Diglycidyl ether of propylene glycol, long chain polyols containing polyoxyalkylene glycols containing polyalkylenes having 2 to 9 carbon atoms (preferably 2 to 4), or polytetramethylene ether glycols Polyglycidyl ether; copolymers of glycidyl (meth) acrylate with free-radically polymerizable monomers such as ethylene, vinyl acetate, or (meth) acrylate, (co) polymers of conjugated diene compounds, or Resulting from the epoxidation of unsaturated carbon bonds in (co) polymers of partial hydrides; polyester resins with epoxy groups, amino methyl groups with urethane bonds or polycaprolactone bonds introduced Acid ester modified epoxy resin or polycaprolactone modified epoxy resin; dimer acid or its derivative with epoxy dimer acid modified epoxy resin; NBR (butadiene-acrylonitrile rubber, (Butadiene-acrylonitrile rubber), CTBN, polybutadiene, acrylic rubber and other rubber components with epoxy-based rubber-modified epoxy resin introduced into the molecule.
作為可撓性環氧樹脂，較佳為下述式(1)所表示之可撓性環氧樹脂。 The flexible epoxy resin is preferably a flexible epoxy resin represented by the following formula (1).
(式中，A為碳數6~14之2價之脂肪族烴基，B為-CH2-或-C(CH3)2-，Ar為經脂肪族烴取代或未經取代之伸苯基，n為1~10之整數)。 (In the formula, A is a divalent aliphatic hydrocarbon group having 6 to 14 carbon atoms, B is -CH 2 -or -C (CH 3 ) 2- , and Ar is an phenylene substituted or unsubstituted by an aliphatic hydrocarbon. , N is an integer from 1 to 10).
作為式(1)所表示之可撓性環氧樹脂，可使用市售品。作為此種市售品，可列舉Japan Epoxy Resins公司製造之YL7175-500(環氧當量487)、YL7150-1000(環氧當量1000)、作為雙酚A型變性環氧樹脂之DIC公司製造之EP-4003S(環氧當量412)、EP-4000S(環氧當量260)等。 As the flexible epoxy resin represented by the formula (1), a commercially available product can be used. Examples of such commercially available products include YL7175-500 (epoxy equivalent 487), YL7150-1000 (epoxy equivalent 1000) manufactured by Japan Epoxy Resins, and EP manufactured by DIC Corporation, which is a bisphenol A type modified epoxy resin. -4003S (epoxy equivalent 412), EP-4000S (epoxy equivalent 260), etc.
丙烯酸系樹脂係分子內具有(甲基)丙烯醯基之化合物，藉由(甲基)丙烯醯基進行反應而形成三次元網狀結構，從而硬化。(甲基)丙烯 醯基較佳為於分子內包含1個以上。 The acrylic resin-based compound has a (meth) acrylfluorenyl group in the molecule, and the (meth) acrylfluorene group reacts to form a three-dimensional network structure, and is hardened. (Meth) acrylic The fluorenyl group is preferably contained in one or more molecules.
作為丙烯酸系樹脂，可列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯、1,2-環己二醇單(甲基)丙烯酸酯、1,3-環己二醇單(甲基)丙烯酸酯、1,4-環己二醇單(甲基)丙烯酸酯、1,2-環己烷二甲醇單(甲基)丙烯酸酯、1,3-環己烷二甲醇單(甲基)丙烯酸酯、1,4-環己烷二甲醇單(甲基)丙烯酸酯、1,2-環己烷二乙醇單(甲基)丙烯酸酯、1,3-環己烷二乙醇單(甲基)丙烯酸酯、1,4-環己烷二乙醇單(甲基)丙烯酸酯、甘油單(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、三羥甲基丙烷單(甲基)丙烯酸酯、三羥甲基丙烷二(甲基)丙烯酸酯、季戊四醇單(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、新戊二醇單(甲基)丙烯酸酯等具有羥基之(甲基)丙烯酸酯、或該等具有羥基之(甲基)丙烯酸酯與二羧酸或其衍生物進行反應而獲得之具有羧基之(甲基)丙烯酸酯等。作為二羧酸，可列舉：草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、順丁烯二酸、反丁烯二酸、鄰苯二甲酸、四氫鄰苯二甲酸、六氫鄰苯二甲酸、及該等之衍生物等。 Examples of the acrylic resin include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate Ester, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,2-cyclohexanediol mono (meth) acrylate, 1,3-cyclohexanediol mono ( (Meth) acrylate, 1,4-cyclohexanediol mono (meth) acrylate, 1,2-cyclohexanedimethanol mono (meth) acrylate, 1,3-cyclohexanedimethanol mono ( (Meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 1,2-cyclohexanediethanol mono (meth) acrylate, 1,3-cyclohexanediethanol mono (Meth) acrylate, 1,4-cyclohexanediethanol mono (meth) acrylate, glycerol mono (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane mono (methyl) Acrylate), trimethylolpropane di (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, neopentyl glycol mono (Meth) acrylates having a hydroxyl group such as (meth) acrylates, Those having a hydroxyl group of (meth) acrylate with a dicarboxylic acid or derivative thereof obtained by reacting a carboxyl group of the (meth) acrylate. Examples of the dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, and fumaric acid. Diacid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and derivatives thereof.
進而，可使用(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸鯨蠟酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸山萮酯、(甲基)丙烯酸2-乙基己酯、其他(甲基)丙烯酸烷基酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸第三丁基環己酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸異基酯、(甲基)丙烯酸縮水甘 油酯、三羥甲基丙烷三(甲基)丙烯酸酯、單(甲基)丙烯酸鋅、二(甲基)丙烯酸鋅、(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸二乙胺基乙酯、新戊二醇(甲基)丙烯酸酯、(甲基)丙烯酸三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、(甲基)丙烯酸2,2,3,3,4,4-六氟丁酯、(甲基)丙烯酸全氟辛酯、(甲基)丙烯酸全氟辛基乙酯、乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸丁氧基乙酯、乙氧基二乙二醇(甲基)丙烯酸酯、甲氧基聚伸烷基二醇單(甲基)丙烯酸酯、辛氧基聚伸烷基二醇單(甲基)丙烯酸酯、十二烷氧基聚伸烷基二醇單(甲基)丙烯酸酯、硬脂醯氧基聚伸烷基二醇單(甲基)丙烯酸酯、烯丙氧基聚伸烷基二醇單(甲基)丙烯酸酯、壬基苯氧基聚伸烷基二醇單(甲基)丙烯酸酯、丙烯醯啉、羥基乙基丙烯醯胺、N,N'-亞甲基雙(甲基)丙烯醯胺、N,N'-伸乙基雙(甲基)丙烯醯胺、1,2-二(甲基)丙烯醯胺乙二醇、二(甲基)丙烯醯氧基甲基三環癸烷、N-(甲基)丙烯醯氧基乙基順丁烯二醯亞胺、N-(甲基)丙烯醯氧基乙基六氫鄰苯二甲醯亞胺、N-(甲基)丙烯醯氧基乙基鄰苯二甲醯亞胺、n-乙烯基-2-吡咯啶酮、苯乙烯衍生物、α-甲基苯乙烯衍生物等。 Furthermore, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, third butyl (meth) acrylate, (formaldehyde) can be used. Base) isodecyl acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, and isomethacrylate Amyl ester, isostearyl (meth) acrylate, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, other alkyl (meth) acrylate, (meth) acrylic ring Hexyl ester, third butyl cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, (meth) acrylic acid different Ester, glycidyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, zinc mono (meth) acrylate, zinc di (meth) acrylate, dimethylamine (meth) acrylate Ethyl ester, diethylaminoethyl (meth) acrylate, neopentyl glycol (meth) acrylate, trifluoroethyl (meth) acrylate, 2,2,3,3-tetramethacrylate Fluoropropyl ester, 2,2,3,3,4,4-Hexafluorobutyl (meth) acrylate, Perfluorooctyl (meth) acrylate, Perfluorooctylethyl (meth) acrylate, Ethylene Alcohol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,4-butanediol Di (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxy diethylene glycol (meth) acrylate, methoxypolyalkylene Diol mono (meth) acrylate, octyloxy polyalkylene glycol mono (meth) acrylate, dodecyloxy polyalkylene glycol mono ( Base) acrylate, stearyl alkoxy polyalkylene glycol mono (meth) acrylate, allyloxy polyalkylene glycol mono (meth) acrylate, nonylphenoxy polyalkylene Diol mono (meth) acrylate, acrylic acid Porphyrin, hydroxyethylacrylamide, N, N'-methylenebis (meth) acrylamide, N, N'-ethylidenebis (meth) acrylamide, 1,2-bis (methyl) Propyl) acrylamide ethylene glycol, bis (meth) acryloxymethyl tricyclodecane, N- (meth) acryloxyethylcis butene difluorene imine, N- (methyl ) Acrylic ethoxyethylhexahydrophthalimide, N- (meth) acrylic ethoxyethylphthalimide, n-vinyl-2-pyrrolidone, styrene Derivatives, α-methylstyrene derivatives, and the like.
又，作為尤佳之丙烯酸系樹脂，可列舉：分子量為100~10000之聚醚、聚酯、聚碳酸酯、聚(甲基)丙烯酸酯且具有(甲基)丙烯醯基之化合物、具有羥基之(甲基)丙烯酸酯、具有羥基之(甲基)丙烯醯胺等。 Examples of particularly preferable acrylic resins include polyethers, polyesters, polycarbonates, poly (meth) acrylates having a molecular weight of 100 to 10,000, compounds having a (meth) acrylfluorenyl group, and hydroxyl groups. (Meth) acrylic acid esters, (meth) acrylamide having hydroxyl groups, and the like.
此處，作為聚醚骨架，較佳為碳數為1~6之有機基經由醚鍵重複而成者，且較佳為不含芳香族環者。為聚醚且具有(甲基)丙烯醯基之化合物可藉由聚醚多元醇與(甲基)丙烯酸或其衍生物之反應而獲 得。 Here, as the polyether skeleton, an organic group having 1 to 6 carbon atoms is preferably repeated through an ether bond, and an aromatic ring is not preferred. Compounds which are polyethers and have a (meth) acryl group can be obtained by reacting a polyether polyol with (meth) acrylic acid or a derivative thereof Got.
作為聚酯骨架，較佳為碳數為1~6之有機基經由酯鍵重複而成者，且較佳為不含芳香族環者。為聚酯且具有(甲基)丙烯醯基之化合物可藉由聚酯多元醇與(甲基)丙烯酸或其衍生物之反應而獲得。 The polyester skeleton is preferably one in which an organic group having 1 to 6 carbon atoms is repeated via an ester bond, and one having no aromatic ring is preferred. The compound which is a polyester and has a (meth) acryl group can be obtained by reacting a polyester polyol with (meth) acrylic acid or a derivative thereof.
作為聚碳酸酯骨架，較佳為碳數為1~6之有機基經由碳酸酯鍵重複而成者，且較佳為不含芳香族環者。為聚碳酸酯且具有(甲基)丙烯醯基之化合物可藉由聚碳酸酯多元醇與(甲基)丙烯酸或其衍生物之反應而獲得。 The polycarbonate skeleton is preferably one in which an organic group having 1 to 6 carbon atoms is repeated via a carbonate bond, and one having no aromatic ring is preferred. A compound which is a polycarbonate and has a (meth) acrylfluorenyl group can be obtained by reacting a polycarbonate polyol with (meth) acrylic acid or a derivative thereof.
作為聚(甲基)丙烯酸酯骨架，較佳為：(甲基)丙烯酸與(甲基)丙烯酸酯之共聚物、具有羥基之(甲基)丙烯酸酯與不具有羧基、羥基等極性基之(甲基)丙烯酸酯之共聚物、具有縮水甘油基之(甲基)丙烯酸酯與不具有極性基之(甲基)丙烯酸酯之共聚物等。 The poly (meth) acrylate skeleton is preferably a copolymer of (meth) acrylic acid and (meth) acrylate, (meth) acrylate having a hydroxyl group, and ( Copolymers of meth) acrylates, copolymers of (meth) acrylates with glycidyl groups and (meth) acrylates without polar groups, and the like.
上述共聚物可分別藉由羧基與具有羥基之(甲基)丙烯酸酯或具有縮水甘油基之(甲基)丙烯酸酯進行反應、羥基與不具有極性基之(甲基)丙烯酸及其衍生物進行反應、縮水甘油基與不具有極性基之(甲基)丙烯酸及其衍生物進行反應而獲得。 The above copolymer can be reacted by a carboxyl group with a (meth) acrylate having a hydroxyl group or a (meth) acrylate with a glycidyl group, and a hydroxyl group with a (meth) acrylic acid having no polar group and a derivative thereof. It is obtained by reacting a glycidyl group with (meth) acrylic acid and its derivatives which do not have a polar group.
而且，為聚(甲基)丙烯酸酯且具有(甲基)丙烯醯基之化合物可藉由聚(甲基)丙烯酸酯多元醇與(甲基)丙烯酸或其衍生物之反應而獲得。 Further, a compound that is a poly (meth) acrylate and has a (meth) acrylfluorene group can be obtained by reacting a poly (meth) acrylate polyol with (meth) acrylic acid or a derivative thereof.
具有羥基之(甲基)丙烯酸酯或(甲基)丙烯醯胺分別係1分子中具有1個以上(甲基)丙烯醯基之(甲基)丙烯酸酯或(甲基)丙烯醯胺，且係含有羥基者。 The (meth) acrylate or (meth) acrylamide having a hydroxyl group is a (meth) acrylate or (meth) acrylamide having one or more (meth) acryl groups in one molecule, respectively, and Those who contain hydroxyl.
具有羥基之(甲基)丙烯酸酯可藉由多元醇化合物與(甲基)丙烯酸衍生物之反應而獲得。該反應可使用公知反應，且相對於多元醇化合物，通常使用0.5~5倍莫耳之丙烯酸酯或丙烯酸。 The (meth) acrylic acid ester having a hydroxyl group can be obtained by reacting a polyol compound with a (meth) acrylic acid derivative. This reaction can use a known reaction, and generally uses 0.5 to 5 times moles of acrylate or acrylic acid relative to the polyol compound.
具有羥基之(甲基)丙烯醯胺可藉由具有羥基之胺化合物與(甲基) 丙烯酸及其衍生物之反應而獲得。關於使(甲基)丙烯酸酯與胺化合物反應而製造(甲基)丙烯醯胺類之方法，由於(甲基)丙烯酸酯之雙鍵極富反應性，故而一般為預先對雙鍵加成胺、環戊二烯、醇等作為保護基，胺化結束後進行加熱使保護基脫離而製造目的物。 (Meth) acrylamide having a hydroxyl group can be obtained by using an amine compound having a hydroxyl group and (meth) Obtained by the reaction of acrylic acid and its derivatives. Regarding a method for producing (meth) acrylamidoamines by reacting a (meth) acrylate with an amine compound, since the double bond of (meth) acrylate is extremely reactive, it is generally to add an amine to the double bond in advance , Cyclopentadiene, alcohol, etc. are used as the protective group, and after the amination is completed, the protective group is detached by heating to produce the target product.
此處，羥基係脂肪族烴基之氫原子被取代之醇性之基，羥基之含量較佳為1分子中為1至50個。 Here, as for the alcoholic group in which the hydrogen atom of a hydroxyl-type aliphatic hydrocarbon group is substituted, the content of a hydroxyl group is preferably 1 to 50 in one molecule.
作為具有此種羥基之丙烯酸系樹脂化合物，例如可列舉下述式(2)~(5)所表示之化合物。 Examples of the acrylic resin compound having such a hydroxyl group include compounds represented by the following formulae (2) to (5).
(式中，R1表示氫原子或甲基，R2表示碳數1~100之2價之脂肪族烴基或具有環狀結構之脂肪族烴基) (In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents a divalent aliphatic hydrocarbon group having 1 to 100 carbon atoms or an aliphatic hydrocarbon group having a cyclic structure.)
(式中，R1及R2分別表示與上述相同者) (Wherein R 1 and R 2 represent the same as those described above)
(式中，R1表示與上述相同者，n表示1~50之整數) (In the formula, R 1 is the same as above, and n is an integer from 1 to 50)
(式中，R1及n分別表示與上述相同者) (Wherein R 1 and n each represent the same as above)
順丁烯二醯亞胺樹脂藉由1分子內含有1個以上之順丁烯二醯亞胺基，並藉由加熱使順丁烯二醯亞胺基反應，從而形成三次元網狀結構而進行硬化。作為順丁烯二醯亞胺樹脂，可列舉：N,N'-(4,4'-二苯甲烷)雙順丁烯二醯亞胺、雙(3-乙基-5-甲基-4-順丁烯二醯亞胺苯基)甲烷、2,2-雙[4-(4-順丁烯二醯亞胺苯氧基)苯基]丙烷等雙順丁烯二醯亞胺樹脂等。 The maleimide resin contains one or more maleimide groups in one molecule, and the maleimide group is reacted by heating to form a three-dimensional network structure. To harden. Examples of the maleimide resin include N, N '-(4,4'-diphenylmethane) bismaleimide and bis (3-ethyl-5-methyl-4). -Bis-butene diimide resins such as cis-butene diimide phenyl) methane, 2,2-bis [4- (4-cis-butene diimide phenoxy) phenyl] propane, etc. .
作為順丁烯二醯亞胺樹脂，更佳為藉由二聚酸二胺與順丁烯二酸酐之反應而獲得之化合物、藉由順丁烯二醯亞胺乙酸、順丁烯二醯亞胺己酸等順丁烯二醯亞胺化胺基酸與多元醇之反應而獲得之化合物。 As the maleimide diimide resin, a compound obtained by a reaction of a dimer acid diamine and maleic anhydride, a maleimide acetic acid, a maleimide A compound obtained by the reaction of a maleic acid such as aminohexic acid with a polyimide and a polyhydric alcohol.
作為順丁烯二醯亞胺樹脂，尤佳為於連結2個順丁烯二醯亞胺基之主鏈具有脂肪族烴基，且該主鏈具有碳數為1以上之烴基。此處，烴基可為直鏈狀、支鏈狀及環狀之任一形態，較佳為碳數為6以上，更佳為碳數為12以上，尤佳為碳數為24以上。又，該烴基較佳為直接鍵結於順丁烯二醯亞胺基。 As the maleimide resin, it is particularly preferred that the main chain connecting two maleimide groups has an aliphatic hydrocarbon group, and the main chain has a hydrocarbon group having a carbon number of 1 or more. Here, the hydrocarbon group may have any of linear, branched, and cyclic forms, and preferably has a carbon number of 6 or more, more preferably a carbon number of 12 or more, and even more preferably a carbon number of 24 or more. The hydrocarbon group is preferably directly bonded to a maleimide group.
作為順丁烯二醯亞胺樹脂，亦可較佳地使用下述式(6)所表示之化合物。 As the maleimide resin, a compound represented by the following formula (6) can also be preferably used.
(式中，Q表示碳數6以上之2價之直鏈狀、支鏈狀、或環狀之脂肪族烴基，P為2價之原子或有機基，且為至少含1個以上選自O、CO、COO、CH2、C(CH3)2、C(CF3)2、S、S2、SO、及SO2中之2價原子或有機基之基，m表示1~10之整數) (In the formula, Q represents a divalent linear, branched, or cyclic aliphatic hydrocarbon group having 6 or more carbon atoms, P is a divalent atom or an organic group, and contains at least one or more selected from O , CO, COO, CH 2 , C (CH 3 ) 2 , C (CF 3 ) 2 , S, S 2 , SO, and SO 2 are divalent atoms or organic radical bases, m represents an integer from 1 to 10 )
此處，P所表示之2價之原子可列舉O、S等，2價之有機基可列舉CO、COO、CH2、C(CH3)2、C(CF3)2、S2、SO、SO2等，另外可列舉至少含有1個以上該等原子或有機基之有機基。作為含有上述原子或有機基之有機基，可列舉具有碳數1~3之烴基、苯環、環、胺基甲酸酯鍵等作為上述以外之結構者，作為該情形時之P，可例示下述化學式所表示之基。 Here, examples of the divalent atom represented by P include O, S, and the like, and examples of the divalent organic group include CO, COO, CH 2 , C (CH 3 ) 2 , C (CF 3 ) 2 , S 2 , SO. , SO 2 and the like, and examples thereof include organic groups containing at least one of these atoms or organic groups. Examples of the organic group containing the atom or the organic group include a hydrocarbon group having 1 to 3 carbon atoms, a benzene ring, a ring, a urethane bond, and the like as structures other than the above. As P in this case, examples can be exemplified. The base represented by the following chemical formula.
若使用主鏈具有脂肪族烴基之雙順丁烯二醯亞胺樹脂，則可獲得耐熱性優異、且於低應力下吸濕後之熱時接著強度良好之半導體接著用熱固化型樹脂組合物，故而較佳。 When a bis-butenediamidine resin having an aliphatic hydrocarbon group in the main chain is used, a thermosetting resin composition for semiconductors having excellent heat resistance and good adhesion strength upon heat absorption under low stress can be obtained. , So it is better.
作為此種順丁烯二醯亞胺樹脂之具體例，可列舉BMI-1500(DESIGNER MOLECULES公司製造，商品名，分子量：1500)、BMI-1700(DESIGNER MOLECULES公司製造，商品名，分子量：1700)等。 Specific examples of such cis-butene diimide resin include BMI-1500 (made by DESIGNER MOLECULES, trade name, molecular weight: 1500), BMI-1700 (made by DESIGNER MOLECULES, trade name, molecular weight: 1700) Wait.
進而，順丁烯二醯亞胺樹脂尤佳為與烯丙基化雙酚與表氯醇之聚合物即烯丙基化環氧樹脂、或者含有羥基之丙烯酸系樹脂併用。 Furthermore, the maleimide resin is particularly preferably used in combination with an allylized epoxy resin, which is a polymer of allylized bisphenol and epichlorohydrin, or an acrylic resin containing a hydroxyl group.
此處，烯丙基化雙酚與表氯醇之聚合物即烯丙基化環氧樹脂例如可如以方式獲得。首先，將多酚化合物溶解於甲醇、異丙醇、正丙醇等醇類或丙酮、甲基乙基酮等酮類等溶劑中。其後，使用氫氧化鈉或氫氧化鉀等鹼，與烯丙基氯或烯丙基溴等烯丙基鹵進行反應而獲得多酚化合物烯丙醚。一面向烯丙基化多酚化合物與表鹵醇類之混合物中一次添加或緩慢添加作為觸媒之氫氧化鈉、氫氧化鉀等鹼金屬氫氧化物之固體，一面於20~120℃下反應0.5~10小時。藉此，可獲得烯丙基化環氧樹脂。 Here, an allylated epoxy resin, which is a polymer of allylated bisphenol and epichlorohydrin, can be obtained, for example, in this manner. First, a polyphenol compound is dissolved in a solvent such as an alcohol such as methanol, isopropanol, and n-propanol, or a ketone such as acetone or methyl ethyl ketone. Thereafter, a base such as sodium hydroxide or potassium hydroxide is used to react with an allyl halide such as allyl chloride or allyl bromide to obtain an allyl ether of a polyphenol compound. It reacts at the temperature of 20 ~ 120 ℃ when it is used to add solids of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide as a catalyst to the mixture of allylized polyphenol compounds and epihalohydrins at one time or slowly. 0.5 ~ 10 hours. Thereby, an allylized epoxy resin can be obtained.
烯丙基化環氧樹脂可較佳地使用下述式(7)所表示之化合物。 As the allylated epoxy resin, a compound represented by the following formula (7) can be preferably used.
(式中，R3~R10分別獨立為選自氫原子、經取代或未經取代之烷基及經取代或未經取代之烯丙基中之基，且其中之至少1個為經取代或未經取代之烯丙基，X為選自SO、SO2、CH2、C(CH3)2、C(CF3)2、O、CO、及COO中之2價之原子或有機基，k為0或1) (Wherein R 3 to R 10 are each independently a group selected from a hydrogen atom, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted allyl group, and at least one of them is substituted Or unsubstituted allyl, X is a divalent atom or organic group selected from SO, SO 2 , CH 2 , C (CH 3 ) 2 , C (CF 3 ) 2 , O, CO, and COO , K is 0 or 1)
於將順丁烯二醯亞胺樹脂與烯丙基化環氧樹脂併用之情形時， 其調配比率較佳為50/50~95/5，更佳為65/35~90/10。 When a maleic acid resin is used in combination with an allylated epoxy resin, The blending ratio is preferably 50/50 ~ 95/5, and more preferably 65/35 ~ 90/10.
於將順丁烯二醯亞胺樹脂與丙烯酸系樹脂併用之情形時，其調配比率較佳為5/95~95/5。 When the maleic acid resin is used in combination with an acrylic resin, the blending ratio is preferably 5/95 to 95/5.
為了改善應力緩和性、密接性等，導電性樹脂組合物亦可含有熱硬化性樹脂以外之樹脂。作為此種樹脂，可列舉：丙烯酸系樹脂、聚酯樹脂、聚丁二烯樹脂、酚樹脂、聚醯亞胺樹脂、聚矽氧樹脂、聚胺基甲酸酯樹脂、二甲苯樹脂等。該等樹脂可單獨使用1種，亦可混合2種以上而使用。熱硬化性樹脂以外之樹脂之含量相對於熱硬化性樹脂100質量份較佳為50質量份以下。 In order to improve stress relaxation properties, adhesion, and the like, the conductive resin composition may contain a resin other than a thermosetting resin. Examples of such resins include acrylic resins, polyester resins, polybutadiene resins, phenol resins, polyimide resins, polysiloxane resins, polyurethane resins, and xylene resins. These resins may be used alone or in combination of two or more. The content of the resin other than the thermosetting resin is preferably 50 parts by mass or less with respect to 100 parts by mass of the thermosetting resin.
(C)成分之硬化劑只要為使熱硬化性樹脂硬化者即可，可單獨使用1種，亦可混合2種以上而使用。例如，作為環氧樹脂之硬化劑，可列舉：雙氰胺、酚樹脂、胺化合物、潛伏性胺化合物、陽離子化合物、酸酐、特殊環氧硬化劑等。該等之中，就硬化性、接著性之觀點而言，較佳為含有選自雙氰胺及酚樹脂中之至少1種。 (C) The hardening | curing agent of a component should just be a thing which hardens | cures a thermosetting resin, It can use individually by 1 type, and can mix and use 2 or more types. Examples of the hardener for epoxy resins include dicyandiamide, phenol resin, amine compounds, latent amine compounds, cationic compounds, acid anhydrides, and special epoxy hardeners. Among these, at least one selected from the group consisting of dicyandiamide and a phenol resin is preferred from the viewpoints of curability and adhesiveness.
硬化劑之含量相對於熱硬化性樹脂100質量份較佳為0.1~100質量份。再者，硬化劑之含量較佳為根據熱硬化性樹脂、硬化劑之種類進行調整。例如，於熱硬化性樹脂為環氧樹脂且硬化劑為酚樹脂之情形時，酚樹脂之含量相對於環氧樹脂100質量份較佳為5~100質量份，更佳為10~100質量份。又，於熱硬化性樹脂為環氧樹脂且硬化劑為雙氰胺之情形時，雙氰胺之含量相對於環氧樹脂100質量份較佳為0.1~10質量份。 The content of the curing agent is preferably 0.1 to 100 parts by mass based on 100 parts by mass of the thermosetting resin. The content of the curing agent is preferably adjusted according to the type of the thermosetting resin and the curing agent. For example, when the thermosetting resin is an epoxy resin and the hardener is a phenol resin, the content of the phenol resin is preferably 5 to 100 parts by mass, and more preferably 10 to 100 parts by mass relative to 100 parts by mass of the epoxy resin. . When the thermosetting resin is an epoxy resin and the curing agent is dicyandiamide, the content of dicyandiamide is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the epoxy resin.
導電性樹脂組合物亦可含有硬化促進劑。作為硬化促進劑，可使用公知之硬化促進劑。例如，於熱硬化性樹脂為環氧樹脂之情形時，作為硬化促進劑，可列舉：咪唑系硬化促進劑、胺系硬化促進劑、三苯基膦系硬化促進劑、二氮雜雙環系硬化促進劑、脲系硬化促進劑、硼酸鹽系硬化促進劑、聚醯胺系硬化促進劑等。該等可單獨使 用1種，亦可混合2種以上而使用。該等之中，就硬化性、接著性之觀點而言，較佳為使用選自咪唑系硬化促進劑及胺系硬化促進劑中之至少1種，較佳為使用咪唑系硬化促進劑。 The conductive resin composition may contain a hardening accelerator. As a hardening accelerator, a well-known hardening accelerator can be used. For example, when the thermosetting resin is an epoxy resin, examples of the hardening accelerator include an imidazole-based hardening accelerator, an amine-based hardening accelerator, a triphenylphosphine-based hardening accelerator, and a diazabicyclic hardening agent. Accelerators, urea-based hardening accelerators, borate-based hardening accelerators, polyamide-based hardening accelerators, and the like. These can be used alone Use 1 type, or you may mix and use 2 or more types. Among these, at least one selected from the group consisting of an imidazole-based hardening accelerator and an amine-based hardening accelerator is preferably used from the viewpoint of hardenability and adhesiveness, and an imidazole-based hardening accelerator is preferably used.
作為咪唑系硬化促進劑，例如可列舉：2-甲基咪唑、2-乙基咪唑、2-異丙基咪唑、2-正丙基咪唑、2-十一烷基-1H-咪唑、2-苯基-4-甲基咪唑(2P4MZ)、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑等。 Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-n-propylimidazole, 2-undecyl-1H-imidazole, 2- Phenyl-4-methylimidazole (2P4MZ), 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and the like.
作為胺系硬化促進劑，例如可列舉：乙二胺、三亞甲基二胺、四亞甲基二胺、六亞甲基二胺、二伸乙基三胺、三伸乙基四胺、四伸乙基五胺等脂肪族胺類；哌啶、哌、薄荷烷二胺、異佛爾酮二胺、1,8-二氮雜雙環(4.5.0)十一烯-7等脂環式及雜環式胺類；鄰苯二胺、間苯二胺、對苯二胺、二胺基二苯甲烷、間苯二甲胺、吡啶、甲基吡啶等芳香族胺類；環氧化合物加成聚胺、麥可加成聚胺、曼尼希加成聚胺、硫脲加成聚胺、酮封阻聚胺等改性聚胺類；雙氰胺、胍、有機酸醯肼、二胺順丁烯二腈、胺醯亞胺、三氟化硼-哌啶錯合物、三氟化硼-單乙基胺錯合物等。就硬化性之觀點而言，更佳為咪唑系硬化促進劑之2-苯基-4-甲基咪唑(2P4MZ)、2-苯基-4,5-二羥基甲基咪唑(2PHZ)、2-苯基-4-甲基-5-羥基甲基咪唑(2P4MHZ)。 Examples of the amine-based hardening accelerator include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetraamine, and tetramine. Aliphatic amines such as ethylenepentamine; piperidine, piperidine , Mentanediamine, isophoronediamine, 1,8-diazabicyclo (4.5.0) undecene-7 and other alicyclic and heterocyclic amines; o-phenylenediamine, m-phenylenediamine Amine, p-phenylenediamine, diaminodiphenylmethane, m-xylylenediamine, pyridine, methylpyridine and other aromatic amines; epoxy compound addition polyamine, Michael addition polyamine, Mannichiga Modified polyamines such as polyamines, thiourea addition polyamines, ketone-blocked polyamines; dicyandiamide, guanidine, organic acid hydrazine, diamine maleimide, nitrile imine, trifluoride Boron-piperidine complex, boron trifluoride-monoethylamine complex, and the like. From the viewpoint of hardenability, 2-phenyl-4-methylimidazole (2P4MZ), 2-phenyl-4,5-dihydroxymethylimidazole (2PHZ), 2 -Phenyl-4-methyl-5-hydroxymethylimidazole (2P4MHZ).
於熱硬化性樹脂為氰酸酯樹脂之情形時，作為硬化促進劑，可使用辛酸鋅、辛酸錫、環烷酸鈷、環烷酸鋅、乙醯丙酮鐵等有機金屬錯合物；氯化鋁、氯化錫、氯化鋅等金屬鹽；三乙基胺、二甲基苄基胺等胺類等。該等硬化促進劑可單獨使用1種，亦可混合2種以上而使用。 When the thermosetting resin is a cyanate resin, as the hardening accelerator, organometallic complexes such as zinc octoate, tin octoate, cobalt naphthenate, zinc naphthenate, iron acetonate, and the like can be used; Metal salts such as aluminum, tin chloride and zinc chloride; amines such as triethylamine and dimethylbenzylamine. These hardening accelerators may be used individually by 1 type, and may mix and use 2 or more types.
於含有硬化促進劑之情形時，其含量根據熱硬化性樹脂之種類而不同，相對於熱硬化性樹脂100質量份較佳為0.1~10質量份，更佳為0.1~5.0質量份。 When a hardening accelerator is contained, the content varies depending on the type of the thermosetting resin, and is preferably 0.1 to 10 parts by mass, and more preferably 0.1 to 5.0 parts by mass, with respect to 100 parts by mass of the thermosetting resin.
導電性樹脂組合物亦可進而含有接著助劑。作為接著助劑，可列舉矽烷偶合劑等。作為接著助劑，較佳為含有下述式(8)所表示之化合物。藉由含有式(8)所表示之化合物作為接著助劑，特別是導電性樹脂組合物之高溫下之接著性或耐回焊性變得良好。 The conductive resin composition may further contain an adhesion promoter. Examples of the bonding aid include a silane coupling agent and the like. As the adhesion promoter, a compound represented by the following formula (8) is preferably contained. By containing the compound represented by Formula (8) as a bonding aid, especially the conductive resin composition has good adhesion at high temperatures or reflow resistance.
(式(8)中，R及R'分別獨立為碳數1~4之烷基，A'為中間可夾有氧原子之碳數3~12之2價之烴基，n為1~3之整數) (In formula (8), R and R 'are each independently an alkyl group having 1 to 4 carbon atoms, A' is a divalent hydrocarbon group having 3 to 12 carbon atoms with an oxygen atom interposed therebetween, and n is 1 to 3 Integer)
作為R、R'，可列舉：甲基、乙基、丙基、異丙基、正丁基、第二丁基、第三丁基等，兩者可彼此相同，亦可不同。作為R，較佳為甲基、乙基。作為R'，較佳為甲基。 Examples of R and R ′ include methyl, ethyl, propyl, isopropyl, n-butyl, second butyl, and third butyl. The two may be the same as or different from each other. R is preferably methyl or ethyl. R 'is preferably a methyl group.
作為A'之2價之烴基，可列舉烴基、或烴基中具有介存氧之醚鍵(-O-)之基等。於A'之2價之烴基之碳數為3以上之情形時，接著性、特別是於高溫下之接著性、吸濕後之高溫下之接著性變得良好。於碳數為12以下之情形時，黏度變低，分散性變得良好。碳數更佳為5~12，進而較佳為7~12。作為烴基，較佳為伸烷基。作為具有醚鍵之基，較佳為-C6H12-O-CH2-、-C8H16-O-CH2-、-C10H20-O-CH2-等。再者，A'之2價之烴基之氫原子之1個或其以上亦可被氟原子、氯原子等鹵素原子等取代。作為n，較佳為2或3，更佳為3。 Examples of the divalent hydrocarbon group of A ′ include a hydrocarbon group or a group having an ether bond (—O—) in which an oxygen is interposed in the hydrocarbon group. When the carbon number of the divalent hydrocarbon group of A ′ is 3 or more, the adhesiveness, especially the adhesiveness at high temperature, and the adhesiveness at high temperature after moisture absorption become good. When the carbon number is 12 or less, the viscosity becomes low, and the dispersibility becomes good. The carbon number is more preferably 5 to 12, and even more preferably 7 to 12. The hydrocarbon group is preferably an alkylene group. As the group having an ether bond, -C 6 H 12 -O-CH 2- , -C 8 H 16 -O-CH 2- , -C 10 H 20 -O-CH 2- , and the like are preferable. Furthermore, one or more of the hydrogen atoms of the divalent hydrocarbon group of A ′ may be substituted with a halogen atom such as a fluorine atom or a chlorine atom. As n, 2 or 3 is preferable, and 3 is more preferable.
進而，為了改善作業性，導電性樹脂組合物亦可含有例如對於環氧樹脂之開環聚合具有反應性之反應性稀釋劑。作為反應性稀釋劑，例如可列舉：正丁基縮水甘油醚、烯丙基縮水甘油醚、2-乙基己基縮水甘油醚、環氧苯乙烷、苯基縮水甘油醚、甲苯基縮水甘油醚、 對第二丁基苯基縮水甘油醚、甲基丙烯酸縮水甘油酯、第三丁基苯基縮水甘油醚、二縮水甘油醚、(聚)乙二醇縮水甘油醚、丁二醇縮水甘油醚、三羥甲基丙烷三縮水甘油醚、1,6-己二醇二縮水甘油醚等。該等可單獨使用1種，亦可混合2種以上而使用。該等之中，更佳為苯基縮水甘油醚、第三丁基苯基縮水甘油醚。反應性稀釋劑之使用量較佳範圍為導電性接著劑組合物之黏度(使用E型黏度計，以3°錐形之條件所測得之值)成為5~200Pa‧s之範圍。 Furthermore, in order to improve workability, the conductive resin composition may contain, for example, a reactive diluent that is reactive to the ring-opening polymerization of the epoxy resin. Examples of the reactive diluent include n-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenylene oxide, phenyl glycidyl ether, and tolyl glycidyl ether. , P-second phenylphenyl glycidyl ether, glycidyl methacrylate, third butylphenyl glycidyl ether, diglycidyl ether, (poly) ethylene glycol glycidyl ether, butanediol glycidyl ether, Trimethylolpropane triglycidyl ether, 1,6-hexanediol diglycidyl ether, and the like. These may be used individually by 1 type, and may mix and use 2 or more types. Among these, phenyl glycidyl ether and third butyl glycidyl ether are more preferred. The preferred range of the amount of the reactive diluent used is that the viscosity of the conductive adhesive composition (a value measured using an E-type viscometer under a condition of a 3 ° cone) becomes a range of 5 to 200 Pa · s.
為了改善作業性，導電性樹脂組合物中亦可含有上述以外之稀釋劑。作為稀釋劑，可使用溶劑類、(甲基)丙烯酸酯化合物等。 In order to improve workability, the conductive resin composition may contain a diluent other than the above. As the diluent, a solvent, a (meth) acrylate compound, or the like can be used.
作為溶劑，例如可列舉：二乙二醇二***、正丁基縮水甘油醚、第三丁基苯基縮水甘油醚、烯丙基縮水甘油醚、2-乙基己基縮水甘油醚、環氧苯乙烷、苯基縮水甘油醚、甲苯基縮水甘油醚、二烷、己烷、甲基溶纖素、環己烷、丁基溶纖素、丁基溶纖素乙酸酯、丁基卡必醇、丁基卡必醇乙酸酯、二乙二醇二甲醚、二丙酮醇、N-甲基吡咯啶酮、二甲基甲醯胺、二甲基乙醯胺、γ-丁內酯、及1,3-二甲基-2-咪唑啶酮等。 Examples of the solvent include diethylene glycol diethyl ether, n-butyl glycidyl ether, third butylphenyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, and epoxybenzene Ethane, phenyl glycidyl ether, tolyl glycidyl ether, di Alkane, hexane, methyl lysin, cyclohexane, butyl lysin, butyl lysin acetate, butyl carbitol, butyl carbitol acetate, diethylene glycol dimethyl ether, Acetone alcohol, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, γ-butyrolactone, and 1,3-dimethyl-2-imidazolidone.
該等稀釋劑可單獨使用1種，亦可混合2種以上而使用。該等稀釋劑較佳為相對於導電性樹脂組合物之固形物成分100質量份添加1~20質量份。 These diluents may be used alone or in combination of two or more. These diluents are preferably added in an amount of 1 to 20 parts by mass based on 100 parts by mass of the solid content of the conductive resin composition.
導電性樹脂組合物可於不違背本發明之宗旨之限度內含有上述成分以外之成分。作為此種成分，可列舉：黏度調整劑、消泡劑、著色劑、阻燃劑等。 The conductive resin composition may contain components other than the above-mentioned components within a limit not deviating from the gist of the present invention. Examples of such a component include a viscosity modifier, a defoamer, a colorant, and a flame retardant.
作為黏度調整劑，可列舉：乙酸溶纖素、乙基溶纖素、丁基溶纖素、丁基溶纖素乙酸酯、丁基卡必醇乙酸酯、丙二醇苯醚、二乙二醇二甲醚、二丙酮醇等。該等黏度調整劑可單獨使用1種，亦可混合2種以上而使用。 Examples of the viscosity adjusting agent include acetinolysin, ethylcellosolvin, butylcellosolvin, butylcellosolve acetate, butylcarbitol acetate, propylene glycol phenyl ether, and diethylene glycol dimethyl ether. , Diacetone alcohol, etc. These viscosity modifiers may be used alone or in combination of two or more.
導電性樹脂組合物例如可藉由使用高速混合機等將包含(A)銀被覆二氧化矽粒子、(B)熱硬化性樹脂、及(C)硬化劑之必需成分、以及視需要添加之任意成分均勻地混合之後，使用分散機、捏合機、三輥研磨機等進行混練，進而進行消泡而製造。 The conductive resin composition may include (A) silver-coated silica particles, (B) a thermosetting resin, and (C) an essential component of a hardener, and optionally added by using a high-speed mixer or the like. After the components are uniformly mixed, they are kneaded using a disperser, a kneader, a three-roll mill, and the like, and then manufactured by defoaming.
導電性樹脂組合物之比重較佳為1.0~3.0。於比重為1.0~3.0之情形時，導電性樹脂組合物之導電性或分散性變得良好。即，若比重成為1.0以上，則導電性樹脂組合物之導電性變得良好。若比重成為3.0以下，則導電性樹脂組合物之分散性或作業性變得良好，導電性樹脂組合物之製造成本亦降低。導電性樹脂組合物之比重更佳為1.3~2.5。 The specific gravity of the conductive resin composition is preferably 1.0 to 3.0. When the specific gravity is 1.0 to 3.0, the conductivity or dispersibility of the conductive resin composition becomes good. That is, when the specific gravity is 1.0 or more, the conductivity of the conductive resin composition becomes good. When the specific gravity is 3.0 or less, the dispersibility or workability of the conductive resin composition becomes good, and the manufacturing cost of the conductive resin composition also decreases. The specific gravity of the conductive resin composition is more preferably 1.3 to 2.5.
導電性樹脂組合物之黏度較佳為5~200Pa‧s。再者，黏度係使用E型黏度計(3°錐形)，於25℃、0.5rpm之條件下進行測定。於黏度為5~200Pa‧s之情形時，導電性樹脂組合物之作業性變得良好。即，於黏度為5Pa‧s以上之情形時，抑制滴液等之產生。又，於黏度為200Pa‧s以下之情形時，分注變得容易，且作業性變得良好。導電性樹脂組合物之黏度更佳為20~180Pa‧s。 The viscosity of the conductive resin composition is preferably 5 to 200 Pa · s. The viscosity was measured at 25 ° C and 0.5 rpm using an E-type viscometer (3 ° cone). When the viscosity is 5 to 200 Pa · s, the workability of the conductive resin composition becomes good. That is, when the viscosity is 5 Pa · s or more, the occurrence of dripping and the like is suppressed. When the viscosity is 200 Pa · s or less, dispensing is facilitated and workability is improved. The viscosity of the conductive resin composition is more preferably 20 to 180 Pa · s.
實施形態之導電性樹脂組合物之拉絲性或滴液較少，作業性優異。又，實施形態之導電性樹脂組合物於半導體元件與支持構件之接著時，導電性、接著性優異。此處，作為支持構件，可列舉銅框架、鍍銀銅框架、PPF(Pre-plated Frame，預鍍框架)框架等。進而，實施形態之導電性樹脂組合物使用壽命較長，且亦可抑制空隙之產生。 The conductive resin composition of the embodiment has less stringiness or dripping, and is excellent in workability. In addition, the conductive resin composition according to the embodiment is excellent in conductivity and adhesion when it is bonded to a semiconductor element and a supporting member. Here, examples of the supporting member include a copper frame, a silver-plated copper frame, a PPF (Pre-plated Frame) frame, and the like. Furthermore, the conductive resin composition of the embodiment has a long service life, and can also suppress the generation of voids.
實施形態之導電性樹脂組合物例如黏度為5~200Pa‧s，硬化物之體積電阻率為1×10-1Ω‧cm以下，於25℃下之接著強度為20N以上，於260℃下之接著強度為6N以上。根據實施形態之導電性樹脂組合物，藉由含有(A)銀被覆二氧化矽粒子、(B)熱硬化性樹脂、及(C)硬化劑作為必需成分，可獲得上述特性。再者，上述特性取決於實施例 中之試驗條件。 The conductive resin composition of the embodiment has, for example, a viscosity of 5 to 200 Pa · s, a volume resistivity of the hardened material of 1 × 10 -1 Ω · cm or less, a bonding strength at 25 ° C. of 20 N or more, and 260 ° C. The subsequent strength is 6N or more. According to the conductive resin composition according to the embodiment, the characteristics described above can be obtained by containing (A) silver-coated silica particles, (B) thermosetting resin, and (C) hardener as essential components. Furthermore, the above characteristics depend on the test conditions in the examples.
繼而，針對本發明之半導體裝置進行說明。 Next, a semiconductor device of the present invention will be described.
圖1係表示本發明之一實施形態之半導體裝置。 FIG. 1 shows a semiconductor device according to an embodiment of the present invention.
半導體裝置1例如具有半導體元件2、導電性樹脂組合物3、支持構件4、接合線5、及密封用樹脂組合物6。此處，導電性樹脂組合物3包含上述實施形態之導電性樹脂組合物。又，支持構件4包含引線框架。關於半導體裝置1，由於半導體元件2與支持構件4藉由包含實施形態之導電性樹脂組合物之導電性樹脂組合物3而接著，故而可靠性、生產性優異。 The semiconductor device 1 includes, for example, a semiconductor element 2, a conductive resin composition 3, a support member 4, a bonding wire 5, and a sealing resin composition 6. Here, the conductive resin composition 3 contains the conductive resin composition of the said embodiment. The support member 4 includes a lead frame. The semiconductor device 1 is excellent in reliability and productivity because the semiconductor element 2 and the support member 4 are bonded by the conductive resin composition 3 including the conductive resin composition of the embodiment.
半導體裝置1例如係如下方式製造。首先，經由導電性樹脂組合物3將半導體元件2積層於支持構件4上，藉由加熱使導電性樹脂組合物3硬化而將半導體元件2與支持構件4藉由導電性樹脂組合物3接著。又，藉由超音波將半導體元件2之電極2a與支持構件4之引線部4a打線接合。其後，藉由密封用樹脂組合物6將該等密封。 The semiconductor device 1 is manufactured, for example, as follows. First, the semiconductor element 2 is laminated on the support member 4 via the conductive resin composition 3, and the conductive resin composition 3 is hardened by heating, and the semiconductor element 2 and the support member 4 are bonded by the conductive resin composition 3. The electrode 2a of the semiconductor element 2 and the lead portion 4a of the support member 4 are wire-bonded by ultrasonic waves. Thereafter, these are sealed with the sealing resin composition 6.
以下，表示本發明之具體實施例。 Hereinafter, specific examples of the present invention will be described.
再者，本發明並不限定於該等實施例。 The present invention is not limited to these examples.
將D50為3.5μm之球狀二氧化矽粒子(龍森公司製造，商品名：US-5)10g進行鹼脫脂、酸中和，進行蝕刻、水洗後，加入於二氯化鈀溶液中，並進行攪拌，從而獲得鈀附著基材粒子。 10 g of spherical silica particles (produced by Ronson, trade name: US-5) with a D 50 of 3.5 μm were subjected to alkali degreasing, acid neutralization, etching, washing with water, and then added to a palladium dichloride solution. Then, stirring was performed to obtain palladium-attached substrate particles.
將該鈀附著基材粒子於去離子水300ml中攪拌3分鐘，添加金屬鎳粒子漿料(三井金屬公司製造，商品名：2020SUS)1g，而獲得鎳粒子附著基材粒子。 The palladium-adhered substrate particles were stirred in 300 ml of deionized water for 3 minutes, and 1 g of a metal nickel particle slurry (manufactured by Mitsui Metals, trade name: 2020SUS) was added to obtain nickel-particle-adhered substrate particles.
將該鎳粒子附著基材粒子利用蒸餾水1000ml進行稀釋，加入鍍敷穩定劑4ml進行攪拌而製成基材粒子混合溶液。其後，對該基材粒 子混合溶液一面攪拌一面緩慢添加硫酸鎳400g/l、次亞磷酸鈉100g/l、檸檬酸鈉100g/l、鍍敷穩定劑6ml之混合溶液150ml，於基材粒子形成鎳覆膜。對鍍敷後之液體進行過濾，並將過濾物進行水洗之後，進行乾燥，從而獲得鎳覆膜基材粒子。 The nickel particles adhering to the substrate particles were diluted with 1000 ml of distilled water, and 4 ml of a plating stabilizer was added and stirred to prepare a substrate particle mixed solution. Thereafter, the substrate particles While mixing the sub-mixed solution, slowly add 150 ml of a mixed solution of nickel sulfate 400 g / l, sodium hypophosphite 100 g / l, sodium citrate 100 g / l, and plating stabilizer 6 ml to form a nickel coating on the substrate particles. The plating liquid was filtered, and the filtered substance was washed with water and then dried to obtain nickel-coated substrate particles.
於對混合有硝酸銀5g、蒸餾水1200ml、苯并咪唑10g之溶液進而混合溶解琥珀酸醯亞胺30g、檸檬酸4g並加入乙醛酸10g進行調整而獲得無電解鍍銀液，向該無電解鍍銀液中投入鎳覆膜基材粒子。於80℃下進行加熱攪拌，進行無電解鍍敷後，進行水洗，並使經醇置換者乾燥，從而獲得球狀銀被覆二氧化矽粒子即粒子-1。 A solution containing 5 g of silver nitrate, 1200 ml of distilled water, and 10 g of benzimidazole was further mixed to dissolve 30 g of ammonium succinate and 4 g of citric acid, and 10 g of glyoxylic acid was added to adjust to obtain an electroless silver plating solution. Nickel-coated substrate particles were charged into the silver liquid. After heating and stirring at 80 ° C., electroless plating was performed, water was washed, and the alcohol-substituted person was dried to obtain spherical silver-coated silicon dioxide particles, which is Particle-1.
粒子-1為縱橫比1.01、比表面積1.5m2/g、D50=3.8μm、比D50/D10=1.8、最大粒徑19μm、比重2.8，銀被覆量為27.3質量%。 Particle-1 had an aspect ratio of 1.01, a specific surface area of 1.5 m 2 / g, D 50 = 3.8 μm, a ratio of D 50 / D 10 = 1.8, a maximum particle size of 19 μm, and a specific gravity of 2.8. The amount of silver coating was 27.3% by mass.
使用D50為8.3μm之球狀二氧化矽粒子(龍森公司製造，商品名：US-10)，與粒子-1同樣地進行無電解鍍敷，而獲得球狀銀被覆二氧化矽粒子即粒子-2。粒子-2為縱橫比1.04、比表面積0.5m2/g、D50=8.5μm、比D50/D10=1.6、最大粒徑32μm、比重3.1，銀被覆量為29.2質量%。 Spherical silicon dioxide particles with a D 50 of 8.3 μm (manufactured by Ronson Corporation, trade name: US-10) were used, and electroless plating was performed in the same manner as in Particle-1 to obtain spherical silver-coated silicon dioxide particles. Particles-2. Particle-2 had an aspect ratio of 1.04, a specific surface area of 0.5 m 2 / g, a D 50 = 8.5 μm, a ratio D 50 / D 10 = 1.6, a maximum particle size of 32 μm, and a specific gravity of 3.1. The amount of silver coating was 29.2% by mass.
將粒子-1之100g調配於混合有1.0質量%之矽烷偶合劑(信越化學工業公司製造，商品名：KBM-403)及甲醇之溶液中，並進行攪拌後，進行過濾、乾燥，而獲得經過藉由矽烷偶合劑之處理之球狀銀被覆二氧化矽粒子即粒子-3。粒子-3為縱橫比1.01、比表面積1.5m2/g、D50=3.8μm、比D50/D10=1.8、最大粒徑24μm、比重2.8，銀被覆量為27.4質量%。 100 g of Particle-1 was prepared in a solution in which 1.0% by mass of a silane coupling agent (manufactured by Shin-Etsu Chemical Industry Co., Ltd., KBM-403) and methanol were mixed, and after stirring, filtration and drying were performed to obtain Spherical silver treated with a silane coupling agent is coated with silica particles, namely particle-3. Particle-3 had an aspect ratio of 1.01, a specific surface area of 1.5 m 2 / g, a D 50 = 3.8 μm, a ratio D 50 / D 10 = 1.8, a maximum particle size of 24 μm, and a specific gravity of 2.8. The amount of silver coating was 27.4% by mass.
將粒子-1之100g放入球磨機中，並加入肉豆蔻酸2g及礦油精200 g，並且加入直徑2mm之氧化鋯球，進行3小時脂肪酸被覆處理，其後進行過濾、乾燥，而獲得經脂肪酸被覆之球狀銀被覆二氧化矽粒子即粒子-4。粒子-4為縱橫比1.01、比表面積1.5m2/g、D50=3.8μm、比D50/D10=1.8、最大粒徑23μm、比重2.8，銀被覆量為27.4質量%。 Put 100g of particles-1 into a ball mill, add 2g of myristic acid and 200g of mineral spirits, and add zirconia balls with a diameter of 2mm to perform a fatty acid coating treatment for 3 hours, and then filter and dry to obtain Fatty-coated spherical silver-coated silicon dioxide particles are Particle-4. Particle-4 had an aspect ratio of 1.01, a specific surface area of 1.5 m 2 / g, D 50 = 3.8 μm, a ratio of D 50 / D 10 = 1.8, a maximum particle size of 23 μm, and a specific gravity of 2.8. The amount of silver coating was 27.4% by mass.
將粒子-4之100g調配於混合有1.0質量%之矽烷偶合劑(信越化學工業公司製造，商品名：KBM-403)及甲醇之溶液中，並進行攪拌之後，進行過濾、乾燥，從而獲得經過藉由矽烷偶合劑之處理之球狀銀被覆二氧化矽粒子即粒子-5。粒子-5為縱橫比1.01、比表面積1.5m2/g、D50=3.8μm、比D50/D10=1.8、最大粒徑22μm、比重2.8，銀被覆量為27.3質量%。 100 g of particles-4 was prepared in a solution containing 1.0% by mass of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-403) and methanol, and after stirring, filtration and drying were performed to obtain Spherical silver treated with a silane coupling agent is coated with silicon dioxide particles, namely particle-5. Particle-5 had an aspect ratio of 1.01, a specific surface area of 1.5 m 2 / g, a D 50 = 3.8 μm, a ratio D 50 / D 10 = 1.8, a maximum particle size of 22 μm, and a specific gravity of 2.8. The amount of silver coating was 27.3% by mass.
使用D50為1.0μm之球狀二氧化矽粒子(Admatechs公司製造，商品名：SO-E3)，與粒子-1同樣地進行無電解鍍敷之後，進行水洗，並使經醇置換者乾燥，而獲得球狀銀被覆二氧化矽粒子即粒子-6。粒子-6為縱橫比1.03、比表面積6.0m2/g、D50=1.9μm、比D50/D10=2.5、最大粒徑18μm、比重2.6，銀被覆量為20.0質量%。 Spherical silica particles (manufactured by Admatechs, trade name: SO-E3) with a D 50 of 1.0 μm were used, and electroless plating was performed in the same manner as in Particle-1, followed by washing with water, and drying the alcohol-substituted ones. Then, spherical silver-coated silica particles, that is, particles-6 were obtained. Particle-6 had an aspect ratio of 1.03, a specific surface area of 6.0 m 2 / g, a D 50 = 1.9 μm, a ratio D 50 / D 10 = 2.5, a maximum particle size of 18 μm, and a specific gravity of 2.6. The amount of silver coating was 20.0% by mass.
使用D50為8.0μm之二氧化矽粒子，與粒子-1同樣地進行無電解鍍敷之後，進行水洗，並使經醇置換者乾燥，而獲得球狀銀被覆二氧化矽粒子即粒子-7。粒子-7為縱橫比1.29、比表面積2.2m2/g、D50=8.5μm、比D50/D10=1.5、最大粒徑72μm、比重4.9，銀被覆量為30.0質量%。 Using silica dioxide particles having a D 50 of 8.0 μm, electroless plating was performed in the same manner as in Particle-1, followed by washing with water and drying with alcohol replacement to obtain spherical silver-coated silica particles, namely Particle-7. . Particle-7 had an aspect ratio of 1.29, a specific surface area of 2.2 m 2 / g, D 50 = 8.5 μm, a ratio of D 50 / D 10 = 1.5, a maximum particle size of 72 μm, and a specific gravity of 4.9. The amount of silver coating was 30.0% by mass.
使用D50為7.0μm之球狀二氧化矽粒子，與粒子-1同樣地進行無電解鍍敷，而獲得銀被覆二氧化矽粒子即粒子-8。粒子-8為縱橫比 1.01、比表面積1.1m2/g、D50=7.6μm、比D50/D10=1.8、最大粒徑46μm、比重2.8，銀被覆量為29.0質量%。 Using spherical silica particles having a D 50 of 7.0 μm, electroless plating was performed in the same manner as in the case of particle-1 to obtain particles-8, which are silver-coated silica particles. Particle-8 had an aspect ratio of 1.01, a specific surface area of 1.1 m 2 / g, D 50 = 7.6 μm, a ratio of D 50 / D 10 = 1.8, a maximum particle size of 46 μm, and a specific gravity of 2.8. The amount of silver coating was 29.0% by mass.
使用D50為4.0μm且D10為0.68μm之球狀二氧化矽粒子，與粒子-1同樣地進行無電解鍍敷，而獲得球狀銀被覆二氧化矽粒子即粒子-9。粒子-9為縱橫比1.03、比表面積4.5m2/g、D50=4.3μm、D10=0.71μm、比D50/D10=6.1、最大粒徑22μm、比重3.0，銀被覆量為30.5質量%。 Using spherical silica particles having a D 50 of 4.0 μm and a D 10 of 0.68 μm, electroless plating was performed in the same manner as in the particle-1, thereby obtaining particles-9, which are spherical silver-coated silicon dioxide particles. Particle-9 has an aspect ratio of 1.03, a specific surface area of 4.5 m 2 / g, D 50 = 4.3 μm, D 10 = 0.71 μm, a ratio D 50 / D 10 = 6.1, a maximum particle size of 22 μm, a specific gravity of 3.0, and a silver coating amount of 30.5. quality%.
再者，縱橫比係藉由掃描式電子顯微鏡SSX-550(島津製作所製造)進行測定。比表面積係藉由流動式比表面積測定裝置Flowsorb II2300(島津製作所製造)進行測定。D50、D10、最大粒徑係根據雷射繞射散射式粒度分佈測定裝置LA-920(堀場製作所製造)進行測定。銀被覆量係根據銀被覆二氧化矽粒子之重量、及藉由硝酸將銀溶解而去除之銀去除二氧化矽粒子之重量而算出。將粒子-1~9之特性彙總示於表1。 The aspect ratio was measured with a scanning electron microscope SSX-550 (manufactured by Shimadzu Corporation). The specific surface area was measured with a flow-type specific surface area measuring apparatus Flowsorb II2300 (manufactured by Shimadzu Corporation). D 50 , D 10 , and the maximum particle diameter were measured using a laser diffraction scattering particle size distribution measuring apparatus LA-920 (manufactured by HORIBA, Ltd.). The amount of silver coating was calculated based on the weight of the silver-coated silicon dioxide particles and the weight of the silver-removed silicon dioxide particles removed by dissolving the silver with nitric acid. The characteristics of the particles-1 to 9 are summarized in Table 1.
以成為表2、4、6所示之組成之方式將各成分充分地調配及混合之後，利用三輥研磨機進行混練而製備導電性樹脂組合物。利用自轉公轉真空消泡裝置將該導電性樹脂組合物進行消泡之後，對各種特性進行評價。將結果示於表3、5、7。再者，於導電性樹脂組合物之製備所使用之各成分之詳細情況如下。 After each component was fully prepared and mixed so that it might become a composition shown in Table 2, 4, and 6, it knead | mixed with the three-roll mill, and the electroconductive resin composition was prepared. After this conductive resin composition was defoamed by a rotation revolution vacuum defoaming device, various characteristics were evaluated. The results are shown in Tables 3, 5, and 7. The details of each component used in the preparation of the conductive resin composition are as follows.
‧熱硬化性樹脂：雙酚A型環氧樹脂(環氧當量185) ‧Thermosetting resin: Bisphenol A epoxy resin (epoxy equivalent 185)
‧熱硬化性樹脂：可撓性環氧樹脂(三菱化學公司製造，商品名：YL7175-500，環氧當量：487，式(1)) ‧Thermosetting resin: Flexible epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name: YL7175-500, epoxy equivalent: 487, formula (1))
‧熱硬化性樹脂：羥基乙基丙烯醯胺(興人製造，商品名：HEAA) ‧Thermosetting resin: hydroxyethyl acrylamide (manufactured by Hingren, trade name: HEAA)
‧熱硬化性樹脂：醯亞胺擴張型雙順丁烯二醯亞胺(DESIGNER MOLECULES公司製造，商品名：BMI-1500，數量平均分子量：1500) ‧Thermosetting resin: fluorene imine-expanded biscis butylene diimide (manufactured by DESIGNER MOLECULES, trade name: BMI-1500, number average molecular weight: 1500)
‧熱硬化性樹脂：烯丙基化雙酚環氧樹脂(日本化藥公司製造，商品名：RE-810NM，環氧當量：223，水解性氯：150ppm(1N KOH-乙醇、二烷溶劑，回流30分鐘)) ‧Thermosetting resin: Allylated bisphenol epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: RE-810NM, epoxy equivalent: 223, hydrolyzable chlorine: 150 ppm (1N KOH-ethanol, two Alkane solvent, reflux for 30 minutes))
‧硬化劑：雙酚F(本州化學公司製造) ‧Hardener: Bisphenol F (manufactured by Honshu Chemical Co., Ltd.)
‧硬化劑：雙氰胺(DICY) ‧Hardener: Dicyandiamide (DICY)
‧聚合起始劑：過氧化二異丙苯(日本油脂公司製造，商品名：Percumyl D，快速加熱試驗中之分解溫度：126℃) ‧Polymerization initiator: Dicumyl peroxide (manufactured by Japan Oil Corporation, trade name: Percumyl D, decomposition temperature in rapid heating test: 126 ° C)
‧硬化促進劑：2-苯基-4-甲基-5-羥基甲基咪唑(四國化成公司製造，商品名：2P4MHZ) ‧Hardening accelerator: 2-phenyl-4-methyl-5-hydroxymethylimidazole (manufactured by Shikoku Chemical Co., Ltd., trade name: 2P4MHZ)
‧接著助劑：縮水甘油氧基辛基三甲氧基矽烷(Shin-Etsu Silicones公司製造，商品名：KBM-4803) ‧Adhesive: Glycidyloxyoctyltrimethoxysilane (manufactured by Shin-Etsu Silicones, trade name: KBM-4803)
‧稀釋劑：第三丁基苯基縮水甘油醚(日本化藥公司製造，商品 名：TGE-H) ‧Diluent: tert-butylphenyl glycidyl ether (manufactured by Nippon Kayaku Co., Ltd., commercial product Name: TGE-H)
‧觸變劑：煙霧狀二氧化矽(Nippon Aerosil公司製造，商品名：Aerosil 200) ‧Thixotropic agent: fumed silica (manufactured by Nippon Aerosil, trade name: Aerosil 200)
‧填充材(薄片狀銀被覆玻璃)：薄片狀銀被覆玻璃(Ecka公司製造，商品名：Ag/flaky glass5/30，縱橫比：1.25，D50：6.0μm，D50/D10：1.7，最大粒徑：28μm，比重：4.6，銀被覆量：30質量%) ‧Filling material (flaky silver-coated glass): Flaky silver-coated glass (manufactured by Ecka, trade name: Ag / flaky glass 5/30, aspect ratio: 1.25, D 50 : 6.0 μm, D 50 / D 10 : 1.7, Maximum particle size: 28 μm, specific gravity: 4.6, silver coating amount: 30% by mass)
‧填充材(薄片狀銀粉)：薄片狀銀粉(福田金屬箔工業公司製造，商品名：AgC-221A，D50：6.6μm，比重：10.5) ‧Filling material (flaky silver powder): Flaky silver powder (manufactured by Fukuda Metal Foil Industries, trade name: AgC-221A, D 50 : 6.6 μm, specific gravity: 10.5)
‧填充材(二氧化矽粉)：熔融二氧化矽(龍森公司製造，商品名：US-5，D50：3.5μm，比重：2.2) ‧Filling material (silica dioxide powder): Fused silica (manufactured by Lonson, trade name: US-5, D 50 : 3.5 μm, specific gravity: 2.2)
‧填充劑(奈米銀粒子)：板型奈米銀粒子(TOKUSEN KOGYO公司製造，商品名：M13，D50：2μm，厚度：50nm以下) ‧Filling agent (nano silver particles): plate-type nano silver particles (manufactured by TOKUSEN KOGYO, trade name: M13, D 50 : 2 μm, thickness: 50 nm or less)
‧填充劑(奈米銀粒子)：球狀奈米銀粒子(MITSUBOSHI BELTING公司製造，商品名：MDot，D50：50nm) ‧Filler (nanosilver particles): spherical nanosilver particles (manufactured by MITSUBOSHI BELTING, trade name: MDot, D 50 : 50nm)
‧填充劑(樹脂粒子)：球狀樹脂粒子(信越化學工業公司製造，商品名：KMP-600，D50：1μm) ‧Filler (resin particles): spherical resin particles (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KMP-600, D 50 : 1 μm)
(1)黏度 (1) viscosity
使用東機產業公司製造之E型黏度計(3°錐形)，於25℃、0.5rpm之條件下進行測定。 The measurement was performed at 25 ° C and 0.5 rpm using an E-type viscometer (3 ° cone) manufactured by Toki Sangyo.
(2)觸變性 (2) Thixotropic
使用東機產業公司製造之E型黏度計(3°錐形)，於25℃、5.0rpm之條件下對黏度進行測定，結合(1)之結果，算出於不同轉數下所測得之黏度之比作為觸變性(黏度(0.5rpm)/黏度(5.0rpm))。 Using an E-type viscosity meter (3 ° cone) manufactured by Toki Sangyo Co., Ltd., the viscosity was measured at 25 ° C and 5.0 rpm, and the result of (1) was used to calculate the viscosity measured at different speed The ratio is taken as thixotropy (viscosity (0.5 rpm) / viscosity (5.0 rpm)).
(3)沈澱性 (3) Precipitability
於注射器中填充導電性樹脂組合物10g，以使注射器垂直之方式設置於25℃培養箱。24小時後，自注射器之上部及下部取出導電性樹脂組合物，並對灰分進行測定。藉由下述所示之式算出沈澱性。若沈澱性大於1.5%，則可判斷為容易沈澱。 A syringe was filled with 10 g of the conductive resin composition, and the syringe was placed in a 25 ° C incubator so that the syringe was vertical. After 24 hours, the conductive resin composition was taken out from the upper part and the lower part of the syringe, and the ash content was measured. Precipitability was calculated by the following formula. If the precipitation is more than 1.5%, it can be judged that it is easy to precipitate.
沈澱性[%]=(注射器下部灰分-注射器上部灰分)/注射器上部灰分×100 Precipitability [%] = (ash content in the lower part of the syringe-ash content in the upper part of the syringe) / ash content in the upper part of the syringe × 100
(4)接著強度 (4) Adhesive strength
將導電性樹脂組合物於鍍銀之銅框架上塗佈20μm之厚度，於其上安裝2mm×2mm之矽晶片，並使其於175℃下硬化1小時。其後，使用晶片剪切強度測定裝置，對25℃及260℃下之熱時晶片剪切強度進行測定。 A conductive resin composition was coated on a silver-plated copper frame to a thickness of 20 μm, and a silicon wafer of 2 mm × 2 mm was mounted thereon, and was cured at 175 ° C. for 1 hour. Thereafter, the wafer shear strength was measured using a wafer shear strength measuring device at the time of heat at 25 ° C and 260 ° C.
(5)體積電阻率 (5) Volume resistivity
以硬化後之厚度成為40μm且寬度成為5mm之方式呈玻璃板狀印刷導電性樹脂組合物，並使其於150℃下硬化1小時後，利用數位萬用錶進行測定。 The conductive resin composition was printed in a glass plate shape with a thickness of 40 μm and a width of 5 mm after curing, and was cured at 150 ° C. for 1 hour, and then measured with a digital multimeter.
(6)作業性 (6) Workability
於注射器中填充導電性樹脂組合物10g，使用Musashi Engineering公司製造之SHOT MASTER，於溫度25℃、濕度35%RH、針徑=0.3mm、吐出壓力7.85N(0.8kgf)、間隙100μm之條件下，進行對矽晶圓基板上之分注試驗。分注試驗係將噴射數設為100發，對產生有因拉絲引起之角傾斜、注射器堵塞、滴液之噴射數(不良數)進行測定。繼而，藉由下述式算出作業性。於作業性大於10%之情形時，可判斷為作業性較差。 A syringe was filled with 10 g of a conductive resin composition, and SHOT MASTER manufactured by Musashi Engineering was used. The temperature was 25 ° C, the humidity was 35% RH, and the needle diameter Under the conditions of 0.3 mm, a discharge pressure of 7.85 N (0.8 kgf), and a gap of 100 μm, a dispensing test on a silicon wafer substrate was performed. In the dispensing test, the number of shots was set to 100, and the number of shots (defective number) in which an angle inclination due to wire drawing, a clogging of a syringe, and dripping were measured was measured. Then, the workability was calculated by the following formula. When the workability is greater than 10%, it can be judged that the workability is poor.
作業性[%]=不良數/100×100 Workability [%] = Defective number / 100 × 100
(7)耐回焊性 (7) Reflow resistance
於經鍍銀之銅框架上塗佈導電性樹脂組合物20μm之厚度，於其上安裝4mm×4mm之矽晶片，並使其於150℃下硬化1小時。其後，使用KYOCERA Chemical公司製造之環氧密封材(商品名：KE-G3000D)，藉由下述[成形條件]使封裝成形。對該封裝進行85℃、相對濕度85%、168小時之吸濕處理之後，進行IR(Infrared Radiation，紅外線)回焊處理(260℃、10秒)。針對處理後之封裝，使用超音波顯微鏡觀察有無產生龜裂、剝離等。針對10個樣品，對產生有龜裂、剝離等之個數(不良品數)進行測定，並藉由下述式算出耐回焊性。於耐回焊性大於30%之情形時，可判斷為耐回焊性較差。 A silver resin plated copper frame was coated with a conductive resin composition to a thickness of 20 μm, and a 4 mm × 4 mm silicon wafer was mounted thereon and cured at 150 ° C. for 1 hour. Thereafter, an epoxy sealing material (trade name: KE-G3000D) manufactured by KYOCERA Chemical was used, and the package was molded under the following [forming conditions]. After the package was subjected to a moisture absorption treatment at 85 ° C. and a relative humidity of 85% for 168 hours, an IR (Infrared Radiation) reflow treatment was performed (260 ° C., 10 seconds). For the package after the treatment, use an ultrasonic microscope to observe the occurrence of cracks and peeling. With respect to 10 samples, the number of occurrences of cracks, peeling, etc. (number of defective products) was measured, and reflow resistance was calculated by the following formula. When the reflow resistance is greater than 30%, it can be judged that the reflow resistance is poor.
耐回焊性[%]=不良品數/樣品總數×100 Reflow resistance [%] = Number of defective products / Total number of samples × 100
(8)耐熱衝擊性 (8) Thermal shock resistance
於經鍍銀之銅框架上塗佈導電性樹脂組合物20μm之厚度，於其上安裝4mm×4mm之矽晶片，並使其於150℃下硬化1小時。其後，使用KYOCERA Chemical公司製造之環氧密封材(商品名：KE-G3000D)，藉由下述[成形條件]使封裝成形。對該封裝進行冷熱循環處理(將自-55℃升溫至150℃並再冷卻至-55℃之操作作為1循環，並進行1000循環)。針對處理後之封裝，使用超音波顯微鏡觀察有無產生龜裂、剝離等。針對10個樣品，對產生有龜裂、剝離等之個數(不良品數)進行測定，並藉由下述式算出耐熱衝擊性。於耐熱衝擊性大於30%之情形時，可判斷為耐熱衝擊性較差。 A silver resin plated copper frame was coated with a conductive resin composition to a thickness of 20 μm, and a 4 mm × 4 mm silicon wafer was mounted thereon and cured at 150 ° C. for 1 hour. Thereafter, an epoxy sealing material (trade name: KE-G3000D) manufactured by KYOCERA Chemical was used, and the package was molded under the following [forming conditions]. This package was subjected to a hot and cold cycle treatment (the operation of increasing the temperature from -55 ° C to 150 ° C and then cooling to -55 ° C as one cycle and performing 1000 cycles). For the package after the treatment, use an ultrasonic microscope to observe the occurrence of cracks and peeling. With respect to 10 samples, the number of occurrences of cracks, peeling, etc. (the number of defective products) was measured, and the thermal shock resistance was calculated by the following formula. When the thermal shock resistance is greater than 30%, it can be judged that the thermal shock resistance is poor.
耐熱衝擊性[%]=不良品數/測定總數×100 Thermal shock resistance [%] = Number of defective products / Total number of measurements × 100
[成形條件] [Forming conditions]
封裝：80pQFP(14mm×14mm×1.6mm厚) Package: 80pQFP (14mm × 14mm × 1.6mm thickness)
晶片：矽晶片 Chip: Silicon chip
引線框架：銅 Lead frame: copper
密封材之成形：175℃，3分鐘 Forming of sealing material: 175 ° C, 3 minutes
後固化：175℃，8小時 Post-curing: 175 ° C, 8 hours
(9)綜合評價 (9) Comprehensive evaluation
基於各評價進行綜合評價。判定基準如下。 Comprehensive evaluation is performed based on each evaluation. The judgment criteria are as follows.
「A」：以下全部條件均滿足者。 "A": All the following conditions are met.
黏度5~200Pa‧s Viscosity 5 ~ 200Pa‧s
觸變性2.0~7.0 Thixotropic 2.0 ~ 7.0
比重1.0~3.0 Specific gravity 1.0 ~ 3.0
沈澱性1.5%以下 Less than 1.5%
接著強度(25℃)20N以上 Adhesive strength (25 ° C) above 20N
接著強度(260℃)6N以上 Adhesive strength (260 ° C) 6N or more
體積電阻率1×10-1Ω‧cm以下 Volume resistivity 1 × 10 -1 Ω‧cm or less
作業性10%以下 Workability below 10%
耐回焊性30%以下 Reflow resistance below 30%
耐熱衝擊性30%以下 Thermal shock resistance below 30%
「AA」：「A」之條件全部滿足，進而以下條件全部滿足者。 "AA": The conditions of "A" are all satisfied, and the following conditions are all satisfied.
接著強度(25℃)120N以上 Adhesive strength (25 ° C) above 120N
接著強度(260℃)22N以上 Adhesive strength (260 ℃) 22N or more
「B」：「A」之條件1個都不滿足者。 "B": None of the conditions of "A" are satisfied.
Claims (12)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW104102152A TWI663608B (en) | 2015-01-22 | 2015-01-22 | Conductive resin composition and semiconductor device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW104102152A TWI663608B (en) | 2015-01-22 | 2015-01-22 | Conductive resin composition and semiconductor device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201628016A TW201628016A (en) | 2016-08-01 |
| TWI663608B true TWI663608B (en) | 2019-06-21 |
Family
ID=57181841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW104102152A TWI663608B (en) | 2015-01-22 | 2015-01-22 | Conductive resin composition and semiconductor device |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI663608B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019187414A1 (en) * | 2018-03-30 | 2019-10-03 | 京セラ株式会社 | Resin composition for bonding electronic components, method for bonding small chip components, method for producing electronic circuit board, and electronic circuit board |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001011503A (en) * | 1999-06-25 | 2001-01-16 | Catalysts & Chem Ind Co Ltd | New conductive fine particle and its use |
| TW201204806A (en) * | 2006-08-22 | 2012-02-01 | Hitachi Chemical Co Ltd | Circuit connecting material, connection structure of circuit member, and method for manufacturing connection structure of circuit member |
| TW201318487A (en) * | 2011-09-20 | 2013-05-01 | Hitachi Chemical Co Ltd | Adhesive composition, film-like adhesive, adhesive sheet, circuit-connected body, method for connecting circuit component, use of adhesive composition, use of film-like adhesive and use of adhesive sheet |
| TW201331252A (en) * | 2011-12-14 | 2013-08-01 | Cheil Ind Inc | Anisotropic conductive film composition, anisotropic conductive film, and semiconductor device |
-
2015
- 2015-01-22 TW TW104102152A patent/TWI663608B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001011503A (en) * | 1999-06-25 | 2001-01-16 | Catalysts & Chem Ind Co Ltd | New conductive fine particle and its use |
| TW201204806A (en) * | 2006-08-22 | 2012-02-01 | Hitachi Chemical Co Ltd | Circuit connecting material, connection structure of circuit member, and method for manufacturing connection structure of circuit member |
| TW201318487A (en) * | 2011-09-20 | 2013-05-01 | Hitachi Chemical Co Ltd | Adhesive composition, film-like adhesive, adhesive sheet, circuit-connected body, method for connecting circuit component, use of adhesive composition, use of film-like adhesive and use of adhesive sheet |
| TW201331252A (en) * | 2011-12-14 | 2013-08-01 | Cheil Ind Inc | Anisotropic conductive film composition, anisotropic conductive film, and semiconductor device |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201628016A (en) | 2016-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107207835B (en) | Conductive resin composition and semiconductor device | |
| TWI701287B (en) | Engineered polymer-based electronic materials | |
| JP5660272B2 (en) | Flip chip semiconductor package connection structure, build-up layer material, sealing resin composition, and circuit board | |
| JP6190653B2 (en) | Conductive resin composition and semiconductor device | |
| JP6675155B2 (en) | Die attach paste for semiconductor and semiconductor device | |
| TWI698488B (en) | Resin composition, conductive resin composition, adhesive, conductive adhesive, electrode forming paste, semiconductor device | |
| JP6455635B2 (en) | Thermally conductive paste and electronic device | |
| WO2016060088A1 (en) | Interlayer filler composition for semiconductor device, and method for manufacturing semiconductor device | |
| JP2013110422A (en) | Adhesive for electronic component and manufacturing method of semiconductor chip package | |
| TWI481685B (en) | Adhesive for electronic parts | |
| JP2016088978A (en) | Conductive resin composition and electronic component device using the same | |
| CN110692126B (en) | Resin composition for bonding electronic component, method for bonding small chip component, electronic circuit board, and method for manufacturing electronic circuit board | |
| KR20110090758A (en) | Conductive adhesive composition for connecting circuit electrodes, circuit connecting material including the conductive adhesive composition, connected circuit structure and method of the connected circuit structure using the circuit connecting material | |
| TWI663608B (en) | Conductive resin composition and semiconductor device | |
| JP2001240838A (en) | Adhesive composition for semiconductor device, and adhesive sheet | |
| JP6455630B2 (en) | Thermally conductive paste and electronic device | |
| JP6134597B2 (en) | Die attach agent | |
| JP6636874B2 (en) | Resin composition for bonding electronic components, bonding method for electronic components, and electronic component mounting substrate | |
| JP2012162710A (en) | Adhesive for semiconductor | |
| JP2016117869A (en) | Resin composition for semiconductor adhesion and semiconductor device | |
| JP6701039B2 (en) | Resin composition for semiconductor adhesion and semiconductor device | |
| TWI664230B (en) | Liquid epoxy resin composition | |
| JP7371792B2 (en) | Conductive paste and semiconductor devices | |
| JP2017045973A (en) | Manufacturing method for semiconductor device | |
| JP2015137287A (en) | Protective film for semiconductor wafer and method for producing semiconductor chip with protective film for semiconductor wafer |